5-Aminoalkylpyrazole derivatives as pesticidal agents

ABSTRACT

The invention relates to 5-aminoalkylaminopyrazole derivatives of formula (I) or salts thereof: wherein the various symbols are as defined in the description, to processes for their preparation, to compositions thereof, and to their use for the control of pests (including arthropods and helminths).

This application is a continuation-in-part application of internationalpatent application Serial No. PCT/2005EP/0002277 filed Mar. 4, 2005,which published as PCT Publication No. WO 2005/090312 on Sep. 29, 2005,which claims benefit of European patent application Serial No.04007023.7 filed Mar. 24, 2004. Reference is also made to U.S. Pat. Nos.6,060,495; 6,060,502 and 6,136,983, U.S. Patent Publication No.US20060135778 and PCT Publication Nos. WO 96/39389, WO 04/049803, WO04/050633, WO 05/090314, WO 06/000311 and WO 06/061147. Reference isalso made to U.S. Pat. Nos. 5,885,607; 6,001,384; 6,083,519; 6,096,329;6,162,820; 6,239,112; 6,395,765; 6,413,542; 6,426,333; 6,482,425;6,562,953; 6,685,954; 6,716,442; 6,867,229; 6,962,713; 6,998,131 and7,001,889, U.S. Patent Publication No. US20050176657 and PCT PublicationNos. WO 97/36485, WO 98/02042, WO 98/07423, WO 00/02567, WO 00/42056, WO01/92281, WO 03/000034 and WO 04/000034.

The foregoing applications, and all documents cited therein or duringtheir prosecution (“appln cited documents”) and all documents cited orreferenced in the appln cited documents, and all documents cited orreferenced herein (“herein cited documents”), and all documents cited orreferenced in herein cited documents, together with any manufacturer'sinstructions, descriptions, product specifications, and product sheetsfor any products mentioned herein or in any document incorporated byreference herein, are hereby incorporated herein by reference, and maybe employed in the practice of the invention. Citation or identificationof any document in this application is not an admission that suchdocument is available as prior art to the present invention.

It is noted that in this disclosure and particularly in the claimsand/or paragraphs, terms such as “comprises”, “comprised”, “comprising”and the like can have the meaning attributed to it in U.S. Patent law;e.g., they can mean “includes”, “included”, “including”, and the like;and that terms such as “consisting essentially of” and “consistsessentially of” have the meaning ascribed to them in U.S. Patent law,e.g., they allow for elements not explicitly recited, but excludeelements that are found in the prior art or that affect a basic or novelcharacteristic of the invention. The embodiments of the presentinvention are disclosed herein or are obvious from and encompassed by,the detailed description. The detailed description, are given by way ofexample and not intended to limit the invention solely to the specificembodiments described.

The invention relates to 5-aminoalkylaminopyrazole derivatives,processes for their preparation, to compositions thereof, and to theiruse for the control of pests (including arthropods and helminths).

The control of insects, arachnids and helminths with 1-arylpyrazolecompounds has been described in, for example, patent publication numbersWO 87/03781, EP 0295117 and U.S. Pat. No. 4,695,308.

However, since modern pesticides must meet a wide range of demands, forexample regarding level, duration and spectrum of action, use spectrum,toxicity, combination with other active substances, combination withformulation auxiliaries or synthesis, and since the occurrence ofresistances is possible, the development of such substances can never beregarded as concluded, and there is constantly a high demand for novelcompounds which are advantageous over the known compounds, at least asfar as some aspects are concerned.

It is an object of the present invention to provide new pesticides whichmay be used in domestic companion animals.

It is advantageous to apply pesticides to animals in oral form so as toprevent the possible contamination of humans or the surroundingenvironment.

Another object of the invention is to provide new pesticides which maybe used in lower dose than existing pesticides.

Another object of the invention is to provide new pesticides which aresubstantially non-emetic.

Another object of the invention is to provide new pesticides which aresafer to the user and the environment.

These objects are met in whole or in part by the present invention.

The present invention provides a compound which is a5-aminoalkylaminopyrazole derivative of formula (I):

wherein:

R¹ is CN, CH₃, CF₃, CSNH₂ or C(═N-Z)—S(O)_(r)-Q;

W is N or C—R ;

R² and R⁸ are each independently halogen, CH₃ or NR⁹R¹⁰;

R³ is (C₁-C₃)-haloalkyl, (C₁-C₃)-haloalkoxy or SF₅;

R⁴ is hydrogen, (C₂-C₆)-alkenyl, (C₂C₆)-haloalkenyl, (C₂-C₆)-alkynyl,(C₂-C₆)-haloalkynyl, (C₃-C₇)-cycloalkyl, CO₂-(C₁-C₆)-alkyl,CO₂(C₃-C₆)-alkenyl, CO₂-(C₂-C₆)-alkynyl, CO₂—(CH₂)_(m)R¹¹,CO₂—(CH₂)_(m)R¹², CHO, CO—(C₃-C₇)-cycloalkyl, COR¹¹, COR¹², SO₂R¹³,(C₁-C₆)-alkyl or CO—(C₁-C₆)-alkyl, which last two mentioned groups areunsubstituted or substituted by one or more R¹⁴ radicals;

R⁵ is (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₂-C₆)-alkenyl,(C₂-C₆)-haloalkenyl, (C₂-C₆)-alkynyl or (C₂-C₆)-haloalkynyl;

A is (C₁-C₆)-alkylene or (C₂-C₆)-alkenylene which groups areunsubstituted or substituted by one or more R¹⁶ radicals; or is(C₂-C₆)-alkylene in which 2, 3 or 4 adjacent carbon atoms form a(C₃-C₇)cycloalkyl ring, the (C₂-C₆)-alkylene or formed(C₃-C₇)-cycloalkyl ring carbon atoms being unsubstituted or substitutedby one or more radicals selected from the group consisting of(C₁-C₆alkyl and halogen;

R⁶ and R⁷ are each independently H, R¹¹, R¹², (C₁-C₆)-alkyl,(C₂-C₆)-alkenyl or (C₂-C₆)-alkynyl, which last three mentioned groupsare unsubstituted or substituted by one or more radicals selected fromthe group consisting of halogen, (C₃-C₇)-cycloalkyl, R¹¹, R¹²,(C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, OR¹¹ and OR¹²; or are each an acylradical; or

R⁶ and R⁷ together with the attached N atom form a four- toseven-membered saturated ring or a five- to seven-membered unsaturatedring, which ring optionally contains one or more additional hetero atomsin the ring which are selected from O, S and N, the ring beingunsubstituted or substituted by one or more radicals selected from thegroup consisting of halogen, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl and oxo,and when present any additional ring N atom is unsubstituted orsubstituted by a (C₁-C₆)-alkyl, CO—(C₁-C₆)alkyl or CH₂R¹¹ radical; or

R⁶ and R⁷ together with the attached N atom form a phthalimido radicalwhich is unsubstituted or substituted by one or more radicals selectedfrom the group consisting of halogen, (C₁-C₆)-alkyl and(C₁-C₆)-haloalkyl; or

when A is (C₁-C₆)-alkylene, R⁷ together with the attached N atom and Amoiety form a four- to seven-membered saturated ring which isunsubstituted or substituted by one or more radicals selected from thegroup consisting of halogen, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl and oxo,and R⁶ is H, (C₁-C₆)-alkyl, CH₂R¹¹, CO—(C₁-C₆)-alkyl orCO₂—(C₁-C₆)-alkyl;

R⁹ and R¹⁰ are each independently H, (C₁-C₆)-alkyl, (C₂-C₆)-alkenyl or(C₂-C₆)-alkynyl, which last three mentioned groups are unsubstituted orsubstituted by one or more radicals selected from the group consistingof halogen, (C₃-C₇)-cycloalkyl, R¹¹, R¹², (C₁-C₆)-alkoxy,(C₁-C₆)-haloalkoxy, OR¹¹ and OR¹²;

R¹¹ is phenyl unsubstituted or substituted by one or more radicalsselected from the group consisting of halogen, (C₁-C₆)-alkyl,(C₁-C₆)-haloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, CN, NO₂,S(O)_(p)R¹⁷ and NR¹⁸R¹⁹;

R¹² is heterocyclyl unsubstituted or substituted by one or more radicalsselected from the group consisting of halogen, (C₁-C₄)-alkyl,(C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, NO₂, CN,CO₂(C₁-C₆)-alkyl, S(O)_(p)R¹⁷, OH and oxo;

R¹³ is (C₃-C₇)-cycloalkyl, (C₂-C₆)-alkenyl, (C₂-C₆)-haloalkenyl,(C₂-C₆)-alkynyl, (C₂-C₆)-haloalkynyl, R¹¹ or R¹²; or is (C₁-C₆)-alkylunsubstituted or substituted by one or more R¹⁴ radicals;

R¹⁴ is halogen, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, (C₃-C₆)-alkenyloxy,(C₃-C₆)-haloalkenyloxy, (C₃-C₆)-alkynyloxy, (C₃-C₆)-haloalkynyloxy,(C₃-C₇)-cycloalkyl, S(O)_(p)R , CN, NO₂, OH, R¹¹, R¹², COR¹⁶ NR⁹R¹⁸ OR¹⁶or CO₂R¹⁶;

R¹⁵ is (C₃-C₇)-cycloalkyl, (C₂-C₆)-alkenyl, (C₂-C₆)-haloalkenyl,(C₁-C₆)-alkynyl, (C₂-C₆)-haloalkynyl, R¹¹ or R¹²; or is.(C₁-C₆)-alkylunsubstituted or substituted by one or more radicals selected from thegroup consisting of halogen, (C₃-C₇)-cycloalkyl, R¹¹ and R¹²;

R¹⁶ is (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₂-C₆)-alkenyl,(C₂-C₆)-haloalkenyl, (C₂-C₆)-alkynyl, (C₂-C₆)-haloalkynyl,(C₃-C₇)-cycloalkyl, (C₃-C₇)-cycloalkyl-(C₁-C₄)-alkyl, (CH₂)_(q)R¹¹ or(CH₂)_(q)R¹²;

R¹⁷ is (C₁-C₆)-alkyl or (C₁-C₆)-haloalkyl;

R¹⁸ and R¹⁹ are each independently H, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl,(C₃-C₆)-alkenyl, (C₃-C₆)-haloalkenyl, (C₃-C₆)-alkynyl,(C₃-C₇)-cycloalkyl or (C₃-C₇)-cycloalkyl-(C₁-C₆>alkyl; or

R¹⁸ and R¹⁹ together with the attached N atom form a five- orsix-membered saturated ring which optionally contains an additionalhetero atom in the ring which is selected from O, S and N, the ringbeing unsubstituted or substituted by one or more radicals selected fromthe group consisting of halogen, (C₁-C₆)-alkyl and (C₁-C₆)-haloalkyl;

Z is H, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₆)-alkenyl,(C₃-C₆)-alkynyl, (CH₂)_(q)R¹¹, COR¹⁷, CO₂—(C₁-C₆)-alkyl or S(O)_(p)R¹⁷;

Q is (C₁-C₆)-alkyl or CH₂R¹¹;

n, p and r are each independently zero, one or two;

m and q are each independently zero or one; and

each heterocyclyl in the above-mentioned radicals is independently aheterocyclic radical having 3 to 7 ring atoms and 1, 2 or 3 hetero atomsin the ring selected from the group consisting of N, O and S;

or a pesticidally acceptable salt thereof.

These compounds possess valuable pesticidal properties.

The invention also encompasses any stereoisomer, enantiomer or geometricisomer, and mixtures thereof.

By the term “pesticidally acceptable salts” is meant salts the anions orcations of which are known and accepted in the art for the formation ofsalts for pesticidal use.

Suitable salts with bases, e.g. formed by compounds of formula (I)containing a carboxylic acid group, include alkali metal (e.g. sodiumand potassium), alkaline earth metal (e.g. calcium and magnesium),ammonium and amine (e.g. diethanolamine, triethanolamine, octylamine,morpholine and dioctylmethylamine) salts. Suitable acid addition salts,e.g. formed by compounds of formula (I) containing an amino group,include salts with inorganic acids, for example hydrochlorides,sulphates, phosphates and nitrates and salts with organic acids forexample acetic acid.

The expression “one or more radicals selected from the group consistingof” in the definition is to be understood as meaning in each case one ormore identical or different radicals selected from the stated group ofradicals, unless specific limitations are defined expressly.

In the present specification, including the accompanying claims, theaforementioned substituents have the following meanings:

Halogen atom means fluorine, chlorine, bromine or iodine.

The term “halo” before the name of a radical means that this radical ispartially or completely halogenated, that is to say, substituted by F,Cl, Br, or I, in any combination, preferably by F or Cl.

Alkyl groups and portions thereof.(unless otherwise defined) may bestraight- or branched-chain.

The expression “(C₁-C₆)-alkyl” is to be understood as meaning anunbranched or branched hydrocarbon radical having 1, 2, 3, 4, 5 or 6carbon atoms, such as, for example a methyl, ethyl, propyl, isopropyl,1-butyl, 2-butyl, 2-methylpropyl or tert-butyl radical.

Alkyl radicals and also in composite groups, unless otherwise defined,preferably have 1 to 4 carbon atoms.

“(C₁-C₆)Haloalkyl” means an alkyl group mentioned under the expression“(C₁-C₆)alkyl” in which one or more hydrogen atoms are replaced by thesame number of identical or different halogen atoms, such asmonohaloalkyl, perhaloalkyl, CF₃, CHF₂, CH₂F, CHFCH₃, CF₃CH₂, CF₃CF₂,CHF₂CF₂, CH₂FCHCl, CH₂Cl, CCl₃, CHCl₂ or CH₂CH₂Cl.

“(C₁-C₆)Alkoxy” means an alkoxy group whose carbon chain has the meaninggiven under the expression “(C₁-C₆)alkyl”. “Haloalkoxy” is, for example,OCF₃, OCHF₂, OCH₂F, CF₃CF20, OCH₂CF₃ or OCH₂CH₂CI. “(C₂-C₆)Alkenyl”means an unbranched or branched non-cyclic carbon chain having a numberof carbon atoms which corresponds to this stated range and whichcontains at least one double bond which can be located in any positionof the respective unsaturated radical. “(C₂-C₆)Alkenyl” accordinglydenotes, for example, the vinyl, allyl, 2-methyl-2-propenyl, 2-butenyl,pentenyl, 2-methylpentenyl or the hexenyl group.

“(C₂-C₆)Alkynyl” means an unbranched or branched non-cyclic carbon chainhaving a number of carbon atoms which corresponds to this stated rangeand which contains one triple bond which can be located in any positionof the respective unsaturated radical. “(C₂-C₆)Alkynyl” accordinglydenotes, for example, the propargyl, 1-methyl-2-propynyl, 2-butynyl or3-butynyl group.

Cycloalkyl groups preferably have from three to seven carbon atoms inthe ring and are optionally substituted by halogen or alkyl.

The expression “(C₃-C₇)-cycloalkyl-(C₁-C₆)-alkyl” means a (C₁-C₆)alkylgroup which is substituted by a (C₃-C₇)cycloalkyl ring.

In compounds of formula (I) the following examples of radicals areprovided:

An example of alkyl substituted by cycloalkyl is cyclopropylmethyl;

an example of alkyl substituted by alkoxy is methoxymethyl (CH₂OCH₃);and

an example of alkyl substituted by alkylthio is methylthiomethyl(CH₂SCH₃).

The expression “(C₁-C₆)-alkylene” is to be understood as meaning anunbranched chain alkanediyl group having from 1 to 6 carbon atoms,,according to the IUPAC Nomenclature of Organic Chemistry 1979, forexample —CH₂, —CH₂CH₂— or —CH₂CH₂CH₂—.

The expression “(C₂-C₆)-alkenylene” is to be understood as meaning anunbranched chain alkenediyl group having from 2 to 6 carbon atoms,according to the IUPAC Nomenclature of Organic Chemistry 1979, forexample —CH═CH—, —CH═CHCH₂— or —CH₂CH═CH—.

A “heterocyclyl” group can be saturated, unsaturated or heteroaromafic;it preferably contains one or more, in particular 1, 2 or 3, heteroatoms in the heterocyclic ring, preferably selected from the groupconsisting of N, O and S; it is preferably an aliphatic heterocyclylradical having 3 to 7 ring atoms or a heteroaromatic radical having 5 to7 ring atoms. The heterocyclic radical can be, for example, aheteroaromatic radical or ring (heteroaryl) such as, for example, amono-, bi- or polycyclic aromatic system in which at least 1 ringcontains one or more hetero atoms, for example pyridyl, pyrimidinyl,pyridazinyl, pyrazinyl, triazinyl, thienyl, thiazolyl, thiadiazolyl,oxazolyl, isoxazolyl, furyl, pyrrolyl, pyrazolyl, imidazolyl andtriazolyl, or it is a partially or fully hydrogenated radical such asoxiranyl, oxetanyl, oxolanyl (=tetrahydrofuryl), oxanyl, pyrrolidyl,piperidyl, piperazinyl, dioxolanyl, oxazolinyl, isoxazolinyl,oxazolidinyl, isoxazolidinyl and morpholinyl. The “heterocyclyl” groupmay be unsubstituted or substituted, preferably by one or more radicals(preferably 1, 2 or 3 radicals) selected from the group consisting ofhalogen, alkoxy, haloalkoxy, alkylthio, hydroxyl, amino, nitro,carboxyl, cyano, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono-and dialkylaminocarbonyl, substituted amino such as acylamino, mono- anddialkylamino, and alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl,haloalkylsulfonyl, alkyl and haloalkyl, and additionally also oxo. Theoxo group can also be present at those hetero ring atoms where variousoxidation numbers are possible, for example in the case of N and S.

An acyl radical is, in a broad sense, the radical of an organic acidwhich is formed formally by removing an OH group, for example theradical of a carboxylic acid and radicals of acids derived therefrom,such as thiocarboxylic acid, unsubstituted or N-substitutediminocarboxylic acids or the radical of carbonic monoesters,unsubstituted or N-substituted carbamic acid, unsubstituted orN-substituted thiocarbamic acid, sulfonic acids, sulfinic acids,phosphonic acids, and phosphinic acids. Acyl is, for example, formyl,alkylcarbonyl such as [(C₁-C₄)alkyl]carbonyl, phenylcarbonyl,alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl,alkylsulfinyl, phenylsulfonyl, N-alkyl-1-iminoalkyl and other radicalsof organic acids. In this context, the radicals can be even furthersubstituted in each of the alkyl or phenyl moieties, for example in thealkyl moiety by one or more radicals selected from the group consistingof halogen, alkoxy, phenyl and phenoxy; examples of substituents in thephenyl moiety are mono- or polysubstituted, preferably up totrisubstituted, identical or different radicals selected from the groupconsisting of halogen, (C₁-C₄)alkyl, (C₁-C₄)alkoxy, (C₁-C₄)haloalkyl,(C₁-C₄)haloalkoxy and nitro, for example o-, m- and p-tolyl,dimethylphenyls, 2-, 3-and 4-chlorophenyl, 2-, 3- and 4-trifluoro- and-trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- andp-methoxyphenyl.

The acyl radical generally has 1 to 24 carbon atoms, preferably 1 to 18,more preferably 1 to 12, most preferably 1 to 7, in particular 1 to 4.

Acyl in the narrower sense is, for example, the radical of an alkanoicacid, alkenoic acid, alkynoic acid, arylcarboxylic acid (for examplebenzoyl), alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl,aryloxycarbonyl, alkylsulfonyl, alkysulfinyl or phenylsulfonyl; in aneven narrower sense, acyl is a radical of an alkanoic acid, for examplea (C₁-C₂₄)alkanoic acid, preferably (C₁-C₈)alkanoic acid, in particular(C₁-C₁₂)alkanoic acid, very especially (C₁-C₆)alkanoic acid such asformyl, acetyl or propionyl.

Preferably acyl is formyl, CO—(C₁-C₆)-alkyl, CO₂—(C₁-C₆)-alkyl orSO₂—(C₁-C₆)-alkyl which last three mentioned groups are unsubstituted orsubstituted by one or more halogen, (C₃-C₇)-cycloalkyl, R¹¹ or R¹²radicals.

The term pests means arthropod pests (including insects and arachnids),and helminths (including nematodes).

In the following preferred definitions it is generally to be understoodthat where symbols are not specifically defined they are to be aspreviously defined in the description.

Preferably R¹ is CN or CSNH₂ (more preferably R¹ is CN).

Preferably W is C-halogen (moreipreferably W is C—Cl).

Preferably R² is Cl.

Preferably R³ is CF₃ or OCF₃ (more preferably R³ is CF₃).

Preferably R⁴ is hydrogen, (C₂-C₆)-alkenyl, (C₂-C₆)-haloalkenyl,(C₂-C₆)-alkynyl, (C₂-C₆)-haloalkynyl, (C₃-C₇)-cycloalkyl,CO₂-(C₁-C₆)-alkyl, CO₂-(C₃-C₆)-alkenyl, CO₂—(C₂-C₆)-alkynyl,CO₂CH₂)_(m)R¹¹, CHO, CO—(C₃-C₇)-cycloalkyl, COR¹¹, COR¹², SO₂R¹³,(C₁-C₆)-alkyl or CO—(C₁-C₆)-alkyl, which last two mentioned groups areunsubstituted or substituted by one or more R¹⁴ radicals.

Preferably R⁵ is CF₃.

Preferably A is (C₁-C₆)-alkylene unsubstituted or substituted by one ormore R¹⁶ radicals, or (C₂-C₆)-alkenylenevunsubstituted or substituted byone or more radicals selected from the group consisting of(C₁-C₃)-alkyl, (C₁-C₃)-haloalkyl, (C₂-C₃)-alkenyl, (C₂-C₃)-alkynyl,(C₃-C₇)-cycloalkyl, (C₃-C₇)-cycloalkyl-(C₁-C₃)-alkyl and (CH₂)_(q)R¹¹(more preferably A is (C₁-C₆)-alkylene).

Preferably R⁶ and R⁷ are each independently H, R¹¹, R¹², (C₁-C₆)-alkyl,(C₂-C₆)-alkenyl or (C₂-C₆)alkynyl, which last three mentioned groups areunsubstituted or substituted by one or more radicals selected from thegroup consisting of halogen, (C₃-C₇)-cycloalkyl, R¹¹, R¹²,(C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, OR¹¹ and OR¹²; or are SO₂R¹⁵,CO—(C₃-C₆)alkenyl, CO₂—(C₂-C₆)-alkynyl, CHO, CO—(C₃-C₇)-cycloalkyl,COR¹¹, COR₁₂, CO—(C₁-C₆)-alkyl or CO₂—(C₁-C₆)-alkyl, which last twomentioned groups are unsubstituted or substituted by one or moreradicals selected from the group consisting of halogen,(C₃-C₇)-cycloalkyl, R¹¹ and R¹²; or

R⁶ and R⁷ together with the attached N atom form a four- toseven-membered saturated ring or a five- to seven-rnembered unsaturatedring, which ring optionally contains one or more additional.hetero atomsin the ring which are selected from O, S and N, the ring beingunsubstituted or substituted by one or more radicals selected from thegroup consisting of halogen, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl and oxo,and when present any additional ring N atom is unsubstituted orsubstituted by a (C₁-C₆)-alkyl, CO—(C₁-C₆)-alkyl or CH₂R¹¹ radical; or

R⁶ and R⁷ together with the attached N atom form a phthalimido radicalwhich is unsubstituted or substituted by one or more radicals selectedfrom the group consisting of halogen, (C₁-C₆)-alkyl and(C₁-C₆chaloalkyl; or when A is (C₁-C₆)-alkylene, R⁷ together with theattached N atom and A moiety form a four- to seven-membered saturatedring which is unsubstituted or substituted by one or more radicalsselected from the group consisting of halogen, (C₁-C₆)-alkyl,(C₁-C₆)-haloalkyl and oxo, and R⁶ is H, (C₁-C₆)-alkyl, CH₂R¹¹,CO—(C₁-C₆)-alkyl or CO₂—(C₁-C₆)-alkyl.

More preferably R⁶ and R⁷ are each independently H, R¹¹, R¹²,(C₁-C₆)-alkyl, (C₂-C₆)-alkenyl or (C₂-C₆)-alkynyl, which last threementioned groups are unsubstituted or substituted by one or moreradicals selected from the group consisting of halogen,(C₃-C₇)cycloalkyl, R¹¹, R¹², (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, OR¹¹and OR¹²; or are SO₂R¹⁵, CO₂—(C₃-C₆)-alkenyl, CO₂—(C₂-C₆)alkynyl, CHO,CO—(C₃-C₇)-cycloalkyl, COR¹¹, COR¹², CO—(C₁-C₆)-alkyl orCO₂-(C₁-C₆)-alkyl, which last two mentioned groups are unsubstituted orsubstituted by one or more radicals selected from the group consistingof halogen, (C₃-C₇)-cycloalkyl, R¹¹ and R¹²; or

R⁶ and R7 together with the attached N atom form a four- toseven-membered saturated ring or a five- to seven-membered unsaturatedring, which ring optionally contains one or more additional hetero atomsin the ring which are selected from O, S and N, the ring beingunsubstituted or substituted by one or more radicals selected from thegroup consisting of halogen, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl and oxo,and when present any additional ring N atom is unsubstituted orsubstituted by a (C₁-C₆)-alkyl, CO—(C₁-C₆)-alkyl or CH₂R¹¹ radical; or

R⁶ and R⁷ together with the attached N atom form a phthalimido radicalwhich is unsubstituted or substituted by one or more radicals selectedfrom the group consisting of halogen, (C₁-C₆)-alkyl and(C₁-C₆)haloalkyl; or

when A is (C₁-C₆)-alkylene, R⁷ together with the attached N atom and Amoiety form a four- to seven-membered saturated ring which isunsubstituted or substituted by one or more radicals selected from thegroup consisting of halogen, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl and oxo,and R⁶ is H, (C₁-C₆)-alkyl, CH₂R¹¹, CO—(C₁-C₆)-alkyl orCO₂-(C₁-C₆)-alkyl.

A preferred class of compounds of formula (I) are those in which:

R¹ is CN;

W is C-halogen;

R² is halogen;

R³ is CF₃, OCF₃ or SF₅;

R⁴ is hydrogen, (C₂-C₆)-alkenyl, (C₂-C₆)-haloalkenyl, (C₂-C₆)-alkynyl,(C₂-C₆)-haloalkynyl, (C₃-C₇)cycloalkyl, CO₂—(C₁-C₆)-alkyl,CO₂—(C₃-C₆)-alkenyl, CO₂—(C₂-C₆)-alkynyl, CO₂—(CH₂)_(m)R¹¹ CHO,CO—(C₃-C₇)-cycloalkyl, COR¹¹, SO₂R¹³ ₁ (C₁-C₅)-alkyl orCO—(C₁-C₆)-alkyl, which last two mentioned groups are unsubstituted orsubstituted by one or more R¹⁴ radicals;

R⁵ is CF₃;

A is (C₁-C₆)-alkylene unsubstituted or substituted by one or more R¹⁶radicals, or (C₂-C₆)-alkenylene unsubstituted or substituted by one ormore radicals selected from the group consisting of (C₁-C₃)-alkyl,(C₁-C₃)-haloalkyl, (C₂-C₃)-alkenyl, (C₂-C₃)-alkynyl, (C₃-C₇)-cycloalkyl,(C₃-C₇)-cycloalkyl-(C₁-C₃)-alkyl and (CH₂)_(q)R¹¹;

R⁶ and R⁷ are each independently H, R¹¹, (C₁-C₆)-alkyl, (C₂-C₆)-alkenylor (C₂-C₆)-alkynyl, which last three mentioned groups are unsubstitutedor substituted by one or more radicals selected from the groupconsisting of halogen, (C₃-C₇)-cycloalkyl, R¹¹, R¹², (C₁-C₆)-alkoxy,(C₁-C₆)-haloalkoxy, OR¹″ and OR¹²; or are SO₂R¹⁵, CO₂—(C₃-C₆)-alkenyl,CO₂-(C₂-C₆)-alkynyl, CHO, CO—(C₃-C₇)-cycloalkyl, COR¹¹, COR¹²,CO—(C₁-C₆)-alkyl or CO₂—(C₁-C₆)-alkyl, which last two mentioned groupsare unsubstituted or substituted by one or rmore radicals selected fromthe group consisting of halogen, (C₃-C₇)-cycloalkyl, R¹¹ and R¹²; or

R⁶ and R⁷ together with the attached N atom form a four- toseven-membered saturated ring or a five- to seven-membered unsaturatedring, which ring optionally contains one or more additional hetero atomsin the ring which are selected from O, S and N, the ring beingunsubstituted or substituted by one or more radicals selected from thegroup consisting of halogen, (C₁-C₃)-alkyl, (C₁-C₃)-haloalkyl and oxo,and when present any additional ring N atom is unsubstituted orsubstituted by a (C₁-C₆)-alkyl, CO—(C₁-C₆)-alkyl or CH₂R¹¹ radical; or

R⁶ and R⁷ together with the attached N atom form a phthalimido radicalwhich is unsubstituted or substituted by one or more radicals selectedfrom the group consisting of halogen, (C₁-C₆)-alkyl and(C₁-C₆)-haloalkyl; or

when A is (C₁-C₆)-alkylene, R⁷ together with the attached N atom and Amoiety form a four- to seven-membered saturated ring which isunsubstituted or substituted by one or more radicals selected from thegroup consisting of halogen, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl and oxo,and R⁶ is H, (C₁-C₆)-alkyl, CH₂R¹¹, CO—(C₁-C₆)-alkyl orCO₂—(C₁-C₆)-alkyl;

R⁹ is H, (C₂-C₃)-alkenyl, (C₂-C₃)-alkynyl or (C₁-C₃)-alkyl, which lastmentioned group is unsubstituted or substituted by an R¹¹ radical;

R¹¹ is phenyl unsubstituted or substituted by one or more radicalsselected from the group consisting of halogen, (C₁-C₃)-alkyl,(C₁-C₃)-haloalkyl, (C₁-C₃)-alkoxy, (C₁-C₃)-haloalkoxy, CN, NO₂,S(O)_(p)R¹⁷ and NR¹⁸R¹⁹;

R¹² is heterocyclyl unsubstituted or substituted by one or more radicalsselected from the group consisting of halogen, (C₁-C₃)-alkyl,(C₁-C₃)-haloalkyl, (C₁-C₃)-alkoxy, (C₁-C₃)-haloalkoxy, NO₂, CN,CO₂(C₁-C₃)-alkyl, S(O)_(p)R¹⁷, OH and oxo;

R¹³ is (C₃-C₇)-cycloalkyl, (C₂-C₃)-alkenyl, (C₂-C₃)-haloalkenyl,(C₂-C₃)-alkynyl, (C₂-C₃)-haloalkynyl, R¹¹ or R¹²; or is (C₁-C₃)-alkylunsubstituted or substituted by one or more R¹⁴ radicals;

R¹⁴ is halogen, (C₁-C₃)-alkoxy, (C₁-C₃)-haloalkoxy, (C₃-C₄)-alkenyloxy,(C₃-C₄)-haloalkenyloxy, (C₃-C₄)-alkynyloxy, (C₃-C₄)-haloalkynyloxy,(C₃-C₇)-cycloalkyl, S(O)_(p)R¹⁶, CN, NO₂, OH, R¹¹, R¹², COR¹⁶ , NR⁹R¹⁸,OR¹⁶ or CO₂R¹⁶;

R¹⁵ is (C₃-C₇)-cycloalkyl, (C₂-C₃)-alkenyl, (C₂-C₃)-haloalkenyl,(C₂-C₃)alkynyl, (C₂-C₃)-haloalkynyl, R¹¹ or R¹²; or is (C₁-C₃)-alkylunsubstituted or substituted by one or more radicals selected from thegroup consisting of halogen, (C₃-C₇)-cycloalkyl, R¹¹ and R¹²;

R¹⁶ is (C₁-C₃)-alkyl, (C₁-C₃)-haloalkyl, (C₂-C₄)-alkenyl,(C₂-C₄)-haloalkenyl, (C₂-C₄)-alkynyl, (C₂-C₄)haloalkynyl,(C₃-C₇)-cycloalkyl, (C₃-C₇)-cycloalkyl-(C₁-C₃)-alkyl, (CH₂)_(q)R¹¹ or(CH₂)_(q)R¹²;

R¹⁷ is (C₁-C₃)alkyl or (C₁-C₃)-haloalkyl;

R¹⁸ and R¹⁹ are each independently H, (C₁-C₃)-alkyl, (C₁-C₃)-haloalkyl,(C₃-C₄)-alkenyl, (C₃-C₄)-haloalkenyl, (C₃-C₄)-alkynyl,(C₃-C₇)-cycloalkyl or (C₃-C₇)-cycloalkyl-(C₁-C₃)-alkyl; or

R¹⁸ and R¹⁹ together with the attached N atom form a five- orsix-membered saturated ring which optionally contains an additionalhetero atom in the ring which is selected from O, S and N, the ringbeing unsubstituted or substituted by one or more radicals selected fromthe group consisting of halogen, (C₁-C₃)-alkyl and (C₁-C₃)-haloalkyl;

n and p are each independently zero, one or two;

m and q are each independently-zero or one; and

each heterocyclyl in the above-mentioned radicals is independently aheterocyclic radical having 3 to 7 ring atoms and 1, 2 or 3 hetero atomsin the ring selected from the group consisting of N, O and S.

A more preferred class of compounds of formula (I) are those in which:

R¹ is CN;

W is C—Cl;

R² is Cl;

R³ is CF₃;

R⁴ is hydrogen, (C₂-C₆)-alkenyl, (C₂-C₆)-haloalkenyl, (C₂-C₆)-alkynyl,(C₂-C₆)-haloalkynyl, (C₃-C₇)-cycloalkyl, CO₂—(C₁-C₆)-alkyl,CO₀₂—(C₃-C₆)-alkenyl, CO₂—(C₂-C₆)-alkynyl, CO₂—(CH₂)_(m)R¹¹, CHO, COR¹¹,SO₂R¹³, (C₁-C₆)-alkyl or CO—(C₁-C₆)-alkyl, which last two mentionedgroups are unsubstituted or substituted by one or more R¹⁴ radicals;

R⁵ is CF₃;

A is (C₁-C₆)-alkylene;

R⁶ and R⁷ are each independently H, R¹¹, (C₁-C₆)-alkyl, (C₂-C₆)-alkenylor (C₂-C₆)-alkynyl, which last three mentioned groups are unsubstitutedor substituted by one or more radicals selected from the groupconsisting of halogen, (C₃-C₆)-cycloalkyl, R¹¹, R¹², (C₁-C₆)-alkoxy,(C₁-C₆)-haloalkoxy, OR¹¹ and OR¹²; or are SO₂R¹⁵, CO₂—(C₃-C₆)-alkenyl,CO₂—(C₂-C₆)-alkynyl, CHO, CO—(C₃-C₆)-cycloalkyl, COR¹¹, CO—(C₁-C₆)-alkylor CO₂—(C₁-C₆)-alkyl, which last two mentioned groups are unsubstitutedor substituted by one or more radicals selected from the groupconsisting of halogen, (C₃-C₆)-cycloalkyl, R¹¹ and R¹²; or

R⁶ and R⁷ together with the attached N atom form a four- toseven-membered saturated ring or a five- to seven-membered unsaturatedring, which ring optionally contains one or more additional hetero atomsin the ring which are selected from O, S and N, the ring beingunsubstituted or substituted by one or more radicals selected from thegroup consisting of halogen, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl and oxo,and when present any additional ring N atom is unsubstituted orsubstituted by a (C₁-C₆)-alkyl, CO—(C₁-C₆)-alkyl or benzyl radical; or

R⁶ and R⁷ together with the attached N atom form a phthalimido radicalwhich is unsubstituted or substituted by one or more radicals selectedfrom the group consisting of halogen, (C₁-C₃)-alkyl and(C₁-C₃)-haloalkyl; or

when A is (C₁-C₆)-alkylene, R⁷ together with the attached N atom and Amoiety form a four- to seven-membered saturated ring which isunsubstituted or substituted by one or more radicals selected from thegroup consisting of halogen, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl and oxo,and R⁶ is H, (C₁-C₆)-alkyl, CH₂R¹¹, CO—(C₁-C₆)-alkyl orCO₂—(C₁-C₆)-alkyl;

R⁹ is H, (C₂-C₃)-alkenyl, (C₂-C₃)-alkynyl or (C₁-C₃)alkyl, which lastmentioned group is unsubstituted or substituted by an R¹¹ radical;

R¹¹ is phenyl unsubstituted or substituted by one or more radicalsselected from the group consisting of halogen, (C₁-C₃)-alkyl,(C₁-C₃)-haloalkyl, (C₁-C₃)-alkoxy, (C₁-C₃)-haloalkoxy, CN, NO₂,S(O)_(p)R¹⁷ and NR¹⁸R¹⁹;

R¹² is heterocyclyl unsubstituted or substituted by one or more radicalsselected from the group consisting of halogen, (C₁-C₃)-alkyl,(C₁-C₃)-haloalkyl, (C₁-C₃)-alkoxy, (C₁-C₃)-haloalkoxy, NO₂, CN,CO₂(C₁-C₃)alkyl, S(O)_(p)R¹⁷, OH and oxo;

R¹³ is (C₃-C₆)cycloalkyl, (C₂-C₃)-alkenyl, (C₂-C₃)-haloalkenyl,(C₂-C₃)-alkynyl, (C₂-C₃)-haloalkynyl, R¹¹ or R¹²; or is (C₁-C₃)alkylunsubstituted or substituted by one or more R¹⁴ radicals;

R¹⁴ is halogen, (C₁-C₃)-alkoxy, (C₁-C₃)-haloalkoxy, (C₃-C₄)-alkenyloxy,(C₃-C₄)-haloalkenyloxy, (C₃-C₄)-alkynyloxy, (C₃-C₄)-haloalkynyloxy,(C₃-C₆)-cycloalkyl, S(O)_(p)R¹⁶, CN, NO₂, OH, R¹¹, R¹², COR¹⁶, NR⁹R¹⁸,OR¹⁶ or CO₂R¹⁶;

R¹⁵ is (C₃-C₆)-cycloalkyl, (C₂-C₃)-alkenyl, (C₂-C₃)-haloalkenyl,(C₂-C₃)-alkynyl, (C₂-C₃)-haloalkynyl, R¹¹ or R¹²; or is (C₁-C₃)-alkylunsubstituted or substituted by one or more radicals selected from thegroup consisting of halogen, (C₃-C₆)-cycloalkyl, R¹¹ and R¹²;

R¹⁶ is (C₁-C₃)-alkyl, (C₁-C₃)-haloalkyl, (C₂C₃)-alkenyl,(C₂C₃)-haloalkenyl, (C₂-C₃)-alkynyl, (C₂-C₃)-haloalkynyl,(C₃-C₈)-cycloalkyl, (C₃-C₆)-cycloalkyl-(C₁-C₃)-alkyl, (CH₂)_(q)R¹¹ or(CH₂)_(q)R¹²;

R¹⁷ is (C₁-C₃)-alkyl or (C₁-C₃)-haloalkyl;

R¹⁸ and R¹⁹ are each independently H, (C₁-C₃)-alkyl, (C₁-C₃)-haloalkyl,(C₃-C₄)-alkenyl, (C₃-C₄)-haloalkenyl, (C₃-C₄)-alkynyl,(C₃-C₆)-cycloalkyl or (C₃-C₆)-cycloalkyl-(C₁-C₃)-alkyl; or

R¹⁸ and R¹⁹ together with the attached N atom form a five- orsix-membered saturated ring which optionally contains an additionalhetero atom in the ring which is selected from O, S and N, the ringbeing unsubstituted or substituted by one or more radicals selected fromthe group consisting of halogen, (C₁-C₃)-alkyl and (C₁-C₃)-haloalkyl;

n and p are each independently zero, one or two;

m and q are each independently zero or one; and

each heterocyclyl in the above-mentioned radicals is independently aheterocyclic radical having 3 to 7 ring atoms and 1, 2 or 3 hetero atomsin the ring selected from the group consisting of N, O and S.

A further more preferred class of compounds of formula (I) are those inwhich:

R¹ is CN;

W is C—Cl;

R² is Cl;

R³ is CF₃;

R⁴ is hydrogen, (C₂-C₆)-alkenyl, (C₂-C₆)-alkynyl, CO₂—(C₁-C₆)alkyl,COHCH₂)_(m)R¹¹, SO₂R¹³, CO—(C₁-C₆)-alkyl, CO—(C₁-C₆)-haloalkyl or(C₁-C₆)alkyl, which last mentioned group is unsubstituted or substitutedby one or more R¹⁴ radicals;

R⁵ is CF₃;

A is (C₁-C₅)-alkylene;

R⁶ and R⁷ are each independently H, R¹¹, (C₂-C₆)-alkenyl,(C₂-C₆)-alkynyl or (C₁-C₆)-alkyl, which last mentioned group isunsubstituted or substituted by one or more radicals selected from thegroup consisting of halogen, (C₃-C₆)-cycloalkyl, R¹¹, R¹²,(C₁-C₆)-alkoxy and OR¹¹; or are SO₂R¹⁵, CO—(C₃-C₆)-cycloalkyl, COR¹¹,CO₂—(C₁-C₆)-alkyl or CO—(C₁-C₆)-alkyl, which last mentioned group isunsubstituted or substituted by one or more radicals selected from thegroup consisting of halogen, (C₃-C₆)-cycloalkyl, R¹¹ and R¹²; or

R⁶ and R⁷ together with the attached N atom form a five- toseven-membered saturated ring or a five- to seven-membered unsaturatedring, which ring optionally contains one or more additional hetero atomsin the ring which are selected from O, S and N, the ring beingunsubsfituted or substituted by one or more radicals selected from thegroup consisting of (C₁-C₆)-alkyl and oxo, and when present anyadditional ring N atom is unsubstituted or substituted by a(C₁-C₆)-alkyl, CO—(C₁-C₆)-alkyl or benzyl radical; or

R⁶ and R⁷ together with the attached N atom form a phthalimido radicalwhich is unsubstituted or substituted by one or more radicals selectedfrom the group consisting of halogen, (C₁-C₃)-alkyl and(C₁-C₃)-haloalkyl; or

when A is (C₁-C₅)-alkylene, R⁷ together with the attached N atom and Amoiety form a five- to seven-membered saturated ring which isunsubstituted or substituted by one or more (C₁-C₆)-alkyl radicals, andR⁶ is H, (C₁-C₆)-alkyl, CH₂R¹¹, CO—(C₁-C₆)-alkyl or CO₂—(C₁-C₆)-alkyl;

R⁹ is H, (C₂-C₃)-alkenyl, (C₂-C₃)-alkynyl or (C₁-C₃)alkyl, which lastmentioned group is unsubstituted or substituted by an R¹¹ radical;

R¹¹ is phenyl unsubstituted or substituted by one or more radicalsselected from the group consisting of halogen, (C₁-C₃)-alkyl,(C₁-C₃)-haloalkyl, (C₁-C₃)-alkoxy, (C₁-C₃) haloalkoxy, CN, NO₂,S(O)_(p)R¹⁷ and NR¹⁸R¹⁹;

R¹² is heterocyclyl unsubstituted or substituted by one or more radicalsselected from the group consisting of halogen, (C₁-C₃)-alkyl,(C₁-C₃)-haloalkyl, (C₁-C₃)-alkoxy, (C₁-C₃)-haloalkoxy, NO₂, CN,CO₂(C₁-C₃)-alkyl, S(O)_(p)R¹⁷, OH and oxo;

R¹³ is R¹¹ or R¹²; or is (C₁-C₃)-alkyl unsubstituted or substituted byone or more R¹⁴ radicals;

R¹⁴ is halogen, (C₁-C₃)-alkoxy, (C₁-C₃)-haloalkoxy, (C₃-C₆)-cycloalkyl,S(O)_(p)R¹⁶, CN, NO₂, OH, R¹¹, R¹², COR¹⁶, NR⁹R¹⁸, OR¹⁶ or CO₂R¹⁶;

R¹⁵ is (C₃-C₆)-cycloalkyl, (C₂-C₃)-alkenyl, (C₂-C₃)-alkynyl or R¹¹; oris (C₁-C₃)-alkyl unsubstituted or substituted by one or more radicalsselected from the group consisting of halogen, (C₃-C₆)-cycloalkyl andR¹¹;

R¹⁶ and R¹⁷ are each independently (C₁-C₃)-alkyl or (C₁-C₃)-haloalkyl;

R¹⁸ and R¹⁹ are each independently H or (C₁-C₃)-alkyl;

n and p are each independently zero, one or two;

m is zero or one; and

each heterocyclyl in the above-mentioned radicals is independently aheterocyclic radical having 3 to 7 ring atoms and 1, 2 or 3 hetero atomsin the ring selected from the group consisting of N, O and S.

A most preferred class of compounds of formula (I) are those in which:

R¹ is CN;

W is C—Cl;

R² is Cl;

R³ is CF₃;

R⁴ is hydrogen, CO₂—(C₁-C₆)-alkyl, CO—(C₁-C₆)-alkyl or (C₁-C₆)-alkyl,which last mentioned group is unsubstituted or substituted by aS(O)_(p)—(C₁-C₆)-alkyl radical;

R⁵ is CF₃;

A is (C₁-C₄)-alkylene;

R⁶ is H, R¹¹, (C₂-C₆)-alkenyl, CO—(C₁-C₆)-alkyl or (C₁-C₆)-alkyl, whichlast mentioned group is unsubstituted or substituted by an R¹¹ radical;

R⁷ is hydrogen or (C₁-C₆)-alkyl; or

R⁶ and R⁷ together with the attached N atom form a five- or six-memberedsaturated ring, which ring optionally contains an additional hetero atomin the ring which is selected from O, S and N, the ring beingunsubstituted or substituted by one or more radicals selected from thegroup consisting of (C₁-C₆)-alkyl and oxo, and when present anyadditional ring nitrogen atom is unsubstituted or substituted by a(C₁-C₆)-alkyl, CO—(C₁-C₆)-alkyl or benzyl radical; or

R⁶ and R₇ together with the attached N atom form a phthalimido radical;or when A is (C₁-C₄)-alkylene, R⁷ together with the attached N atom andA moiety forms a five- or six-membered saturated ring, which isunsubstituted or substituted by one or more (C₁-C₆)-alkyl radicals, andR⁶ is H, (C₁-C₆)-alkyl, benzyl, CO—(C₁-C₆)-alkyl or CO₂—(C₁-C₆)-alkyl;

R¹¹ is phenyl unsubstituted or substituted by one or more radicalsselected from the group consisting of halogen, (C₁-C₃)-alkyl,(C₁-C₃)-haloalkyl, (C₁-C₃)-alkoxy (most preferably R¹¹ is phenyl); and

n and p are each independently zero, one or two.

The compounds of general formula (I) can be prepared by the applicationor adaptation of known methods (i.e. methods heretofore-used ordescribed in the chemical literature.

In the following description of processes when symbols appearing informulae are not specifically defined, it is understood that they are“as defined above” in accordance with the first definition of eachsymbol in the specification.

According to a further feature of the invention compounds of formula (I)wherein R¹ is CN, CH₃ or CF₃, and R², R³, R⁴, R⁵, R⁶, R⁷ ₁, W, A and nare as defined above, may be prepared by the reaction of a compound offormula (II):

wherein R¹ is CN, CH₃ or CF₃ and the other values are as defined above,with an alkylating agent of formula (III):R⁶R⁷N-A-L   (III)

wherein R⁶, R⁷ and A are as defined above, and L is a leaving groupgenerally halogen and preferably chlorine, bromine or iodine, and abase. The reaction is generally carried out using a solvent such astetrahydrofuran, dioxan or acetonitrile, at a temperature of from 20° C.to 120° C. The base is preferably an alkali metal hydride such as sodiumhydride, or an alkali metal carbonate such as potassium carbonate orsodium carbonate, or an alkali metal phosphate such as potassiumphosphate, or an organic base such as a tertiary amine, for exampletriethylamine or ethyldiisopropylamine (alkali metal phosphates such aspotassium phosphate are particularly preferred).

According to a further feature of the invention compounds of formula (I)wherein R¹ is CN, CH₃ or CF₃, and R², R³, R⁴, R⁵, R⁶, R⁷, W, A and n areas defined above, may be prepared by the reaction of a compound offormula (IV):

wherein L¹ is a leaving group generally halogen and preferably chlorine,bromine or iodine, and the other values are as defined above, with acompound of formula (V):R⁶R⁷N—H   (V)

wherein R⁶ and R⁷ are as defined above. The reaction is preferablyperformed in the presence of a base such as an alkali metal hydride forexample sodium hydride, or an alkali metal carbonate such as potassiumcarbonate or sodium carbonate, or an organic base such as a tertiaryamine,-for example triethylamine or ethyldiisopropylamine, andoptionally in the presence of a catalyst, preferably an alkali metaliodide such as sodium iodide. Solvents such as tetrahydrofuran, dioxanor acetonitrile are preferably employed, at a reaction temperature offrom 20° C. to 150° C.

According to a further feature of the invention compounds of formula (I)wherein R¹ is CN, CH₃ or CF₃, and R², R³, R⁴, R⁵, R⁶, R⁷, W, A and n areas defined above, may be prepared by the reaction of a compound offormula (VI):

wherein L² is a leaving group generally halogen and preferably bromine,and the other values are as defined above, with a compound of formula(VII):R⁶R⁷N-A-NHR⁴   (VII)

wherein R⁴, R⁶, R⁷ and A are as defined above. The reaction ispreferably performed in the presence of a base such as an alkali metalhydride such as sodium hydride, or an alkali metal carbonate such aspotassium carbonate or sodium carbonate, or an organic base such as atertiary amine, for example triethylamine or ethyldiisopropylamine, in asolvent such as tetrahydrofuran, dioxan or acetonitrile, at atemperature of from 20° C. to 150° C.

According to a further feature of the invention compounds of formula (I)wherein R¹ is CN, CH₃ or CF₃, n is 1 or 2, and R², R³, R⁴, R⁵, R⁶, R⁷, Wand A are as defined above, may be prepared by oxidising a correspondingcompound in which n is 0 or 1. The oxidation is generally performedusing a peracid such as 3-chloroperbenzoic acid in a solvent such asdichloromethane or 1,2-dichloroethane, at a temperature of from 0° C. tothe reflux temperature of the solvent.

According to a further feature of the invention compounds of formula (I)wherein R¹ is CSNH₂, and R², R³, R⁴, R⁵, R⁶, R⁷, W, A and n are asdefined above, may be prepared by the reaction of the correspondingcompound of formula (I) wherein R¹ is CN, with an alkali or alkalineearth metal hydrosulfide, such as lithium, potassium, calcium orpreferably sodium hydrosulfide, in an inert solvent for exampleN,N-dimethylformamide, pyridine, dioxan, tetrahydrofuran, sulfolane,dimethyl sulfoxide, methanol or ethanol at a temperature from −35° C. to50° C. preferably 0° C. to 30° C. Optionally the hydrosulfide may begenerated in situ by treatment with H₂S in the presence of an organicbase, such as a metal alkoxide or trialkylamine or an inorganic base,such as an alkaline or alkaline earth metal hydroxide or a carbonate,such as sodium, potassium or ammonium carbonate. The use of a metalcomplexing agent, such as a crown ether, can be of benefit inaccelerating the reaction. The reaction of the hydrosulfide salt withthe compound of formula (I) wherein R¹ i s CN can also be conducted in atwo-phase water/organic solvent system using a phase transfer catalystsuch as a crown ether or a tetraalkylammonium salt such astetra-n-butylammonium bromide or benzyltrimethylammonium chloride.Organic solvents suitable for use in a two-phase system with waterinclude benzene, toluene, dichloromethane, 1-chlorobutane and methyltertiary-butyl ether. Altematively compounds of formula (I) wherein R¹is CSNH₂, may also be prepared from the corresponding compound offormula (I) wherein R¹ is CN, by treatment with the reagent Ph₂PS₂, forexample as described in Tet. Lett., 24 (20), 2059 (1983).

According to a further feature of the invention compounds of formula (I)wherein R¹ is CSNH₂, and R², R³, R⁴, R⁵, R⁶, R⁷, W, A and n are asdefined above, may be prepared by the reaction of the correspondingcompound of formula (I) wherein R¹ is CN, with abis(trialkylsilyl)sulfide, preferably bis(trimethylsilyl)sulfide, in thepresence of a base generally an alkali metal alkoxide such as sodiummethoxide, in a solvent such as N,N-dimethylformamide, at a temperatureof from 0° C. to 60° C. The procedure is generally described by Lin, Kuand Shiao in Synthesis 1219 (1992).

According to a further feature of the invention compounds of formula (I)wherein R¹ is C(═N—H)—S-Q, and Q, R², R³, R⁴, R⁵, R⁶, R⁷, W, A and n areas defined above, may be prepared by the reaction of the correspondingcompound of formula (I) wherein R¹ is CSNH₂ with an alkylating agent offormula (VIII) or (IX):Q-L³   (VIII)Q₃O⁺BF₄ ⁻  (IX)

wherein Q is as defined above and L³ is a leaving group, generallyhalogen and preferably chlorine, bromine or iodine. The reaction isgenerally performed in the presence of a base, for example:an alkalimetal hydride such as sodium hydride, or an alkali metal alkoxide suchas potassium tert-butoxide, in an inert solvent such as tetrahydrofuranat a temperature from 0 to 60° C. Alternatively an alkali metalcarbonate such as potassium carbonate, or an organic base such as atrialkylamine, for example triethylamine or N,N-diisopropylethylaminemay be used, in an inert solvent such as acetone, at a temperature from0° C. to the reflux temperature of the solvent. When a compound offormula (IX) such as trimethyloxonium tetrafluoroborate is used as thealkylating agent, the base is preferably an alkali metal bicarbonatesuch as sodium bicarbonate, the solvent is for example dichloromethane,and the temperature is from 0° C. to the reflux temperature of thesolvent.

According to a further feature of the present invention compounds offormula (I) wherein R¹ is C(═N-Z)-S-Q, Z is as defined above with theexclusion of H, and Q, R², R³, R⁴, R⁵, R⁶, R⁷, W, A and n are as definedin formula (I), may be prepared by the alkylation, acylation orsulfonylation of the corresponding compound of formula (I) wherein Z isH, with a compound of formula (X):Z-L⁴   (X)

wherein Z is as defined above with the exclusion of H, and L⁴ is aleaving group. For alkylations, where Z is (C₁-C₆))-alkyl,(C₁-C₆)-haloalkyl, (C₃-C₆)-alkenyl, (C₃-C₆)-alkynyl or(CH₂)_(q)R^(11l , L) ⁴ is preferably halogen, alkylsulfonyloxy orarylsulfonyloxy (more preferably chlorine, bromine, iodine,methylsulfonyloxy or p-toluenesulfonyloxy). A base is optionally presentin the reaction which is generally performed in an inert solvent such astetrahydrofuran, dioxan, acetonitrile, toluene, diethyl ether,dichloromethane, dimethylsulfoxide or N,N-dimethylformamide, at atemperature of from −30° C. to 200° C. , preferably at 20° C. to 100° C.The base is generally an alkali metal hydroxide such as potassiumhydroxide, an alkali metal hydride such as sodium hydride, an alkalimetal carbonate such as potassium carbonate or sodium carbonate, analkali metal alkoxide such as sodium methoxide, an alkaline earth metalcarbonate such as calcium carbonate, or an organic base such as atertiary amine, for example triethylamine or ethyidiisopropylamine, orpyridine, or 1,8-diazabicyclo[5.4.0]undec-7-en (DBU).

For acylations, where Z is COR¹⁷ or CO(C₁-C₆)-alkyl, (X) is preferablyan acid halide where L⁴ is preferably chlorine or bromine (morepreferably chlorine). A base is optionally present in the reaction,which is generally performed using similar bases, solvents andtemperatures as employed for the alkylations. For sulfonylations, whereZ is SO₂R¹⁷, (X) is preferably a sulfonyl halide where L⁴ is preferablychlorine or bromine (more preferably chlorine). A base is optionallypresent in the reaction, which is generally performed using similarbases, solvents and temperatures as employed for the alkylations.

Intermediates of formula (IV) above, may be prepared by the reaction ofa compound of formula (II) as defined above, with a compound of formula(XI):L¹-A-L⁵   (XI)

wherein L¹ and L⁵ are leaving groups as defined above, preferablywherein L⁵ is chosen to be more reactive than L¹, for example wherein L⁵is bromo and L¹ is chloro, in the presence of a base and a solvent suchas tetrahydrofuran, at a temperature of from 30° C. to 120° C. The baseis for example as sodium hydride, or an alkali metal carbonate such aspotassium carbonate or sodium carbonate, or an organic base such as atertiary amine, for example triethylamine or ethyidiisopropylamine.

Collections of compounds of the formula (I) which can be synthesized bythe above mentioned process may also be prepared in a parallel manner,and this may be effected manually or in a semiautomated or fullyautomated manner. In this case, it is possible, for example, to automatethe procedure of the reaction, work-up or purification of the productsor of the intermediates. In total, this is to be understood as meaning aprocedure as is described, for example, by S. H. DeWitt in “AnnualReports in Combinatorial Chemistry and Molecular Diversity: AutomatedSynthesis”, Volume 1, Verlag Escom 1997, pages 69 to 77.

A series of commercially available apparatuses as are offered by, forexample, Stem Corporation, Woodrolfe Road, Tollesbury, Essex, CM9 8SE,England or H+P Labortechnik GmbH, Bruckmannring 28, 85764Oberschleilheim, Germany or Radleys, Shirehill, Saffron Walden, Essex,England, may be used for the parallel procedure of the reaction andwork-up. For the parallel purification of compounds of the formula (I),or of intermediates obtained during the preparation, use may be made,inter alia, of chromatography apparatuses, for example those by ISCO,Inc., 4700 Superior Street, Lincoln, Nebr. 68504, USA.

The apparatuses mentioned lead to a modular procedure in which theindividual process steps are automated, but manual operations must beperformed between the process steps. This can be prevented by employingsemi-integrated or fully integrated automation systems where theautomation modules in question are operated by, for example, robots.Such automation systems can be obtained, for example, from ZymarkCorporation, Zymark Center, Hopkinton, Mass. 01748, USA.

In addition to what has been described here, compounds of the formula(I) may be prepared in part or fully by solid-phase-supported methods.For this purpose, individual intermediate steps or all intermediatesteps of the synthesis or of a synthesis adapted to suit the procedurein question are bound to a synthetic resin. Solid-phase-supportedsynthesis methods are described extensively in the specialistliterature, for example Barry A. Bunin in “The Combinatorial Index”,Academic Press, 1998.

The use of solid-phase-supported synthesis methods permits a series ofprotocols which are known from the literature and which, in turn, can beperformed manually or in an automated manner. For example, the “tea-bagmethod” (Houghten, U.S. Pat. No. 4,631,211; Houghten et al., Proc. Natl.Acad. Sci, 1985, 82, 5131-5135), in which products by IRORI, 11149 NorthTorrey Pines Road, La Jolla, Calif. 92037, USA, are employed, may besemiautomated. The automation of solid-phase-supported parallelsyntheses is performed successfully, for example, by apparatuses byArgonaut Technologies, Inc., 887 Industrial Road, San Carlos, Calif.94070, USA or MultiSynTech GmbH, Wullener Feld 4, 58454 Witten, Germany.

The preparation of the processes described herein yields compounds ofthe formula (I) in the form of substance collections which are termedlibraries. The present invention also relates to libraries whichcomprise at least two compounds of the formula (I).

Compounds of formula (II), (III), (IV), (V), (VI), (VII), (VIII), (IX),(X) and (XI) are known or may be prepared by known methods.

The following non-limiting Examples illustrate the preparation of thecompounds of formula (I).

CHEMICAL EXAMPLES

NMR spectra were run in deuterochloroform unless stated otherwise. Inthe Examples which follow, quantities (also percentages) are weightbased, unless stated otherwise.

Example 15-[N-Methyl-N-(phthalimidomethyl)amino]-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulfinylpyrazole(Compound number 1-53)

N-Bromomethylphthalimide (0.19 g, 0.80 mmol) was added to a mixture of1-(2,6-dichloro-4-trifluoromethylpheny)-3-cyano-5-methylamino4-trifluoromethylsulflnylpyrazole(0.3 g, 0.67 mmol) and tripotassium phophate (0.42 g, 2.0 mmol) inacetonitrile (10 ml), and the mixture heated under reflux for 6 hours.

After extractive workup (heptane-ethyl acetate, water) andchromatography the title product was obtained (0.29 g); mp. 163° C.; 1H-NMR: 2.99 (3H), 4.71 (2H), 7.77 and 7.87 (4H), 7.82 (2H); 19F-NMR:−63.8;-72.2 ppm.

Example 21-(2,6-Dichloro-4-trifluoromethylphenyl)-3-cyano-5-(2-diethylaminoethyl)amino-4-trifluoromethylsulfinylpyrazole(Compound number 2-50)

2-Chloroethyl-diethylammonium chloride.(0.19 g, 1.1 mmol) was added to amixture of5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulfinylpyrazole(0.4 g, 0.92 mmol) and tripotassium phosphate (0.77 g, 3.7 mmol) inacetonitrile (6 ml), and the mixture heated under reflux for 6 hours.After extractive workup (heptane-ethyl acetate, water) andchromatography the title product was obtained (0.15 g); 1H-NMR: 0.87(3H), 2.40 (2H), 2.53 (2H), 2.98 (2H), 7.80 (2H); 19F-NMR: -64.2; −74.5ppm.

Example 3 1-Dichloro-4-trifluoromethylpheno)-3-cyano-4-trifluoromethylthio-5[N-(3-dimethylaminopropyl)-N-methylamino]pyrazole(Compound number 546)

Dimethylamine solution 60% (0.12 g, 1.6 mmol) in tetrahydrofuran (4 ml)was added to a mixture of5-(3-chloropropyl)methylamino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4trifluoromethylthiopyrazole(0.2 g, 0.39 mmol) and sodium iodide (0.12 g, 0.8 mmol), and the mixtureheated at 150° C. for 30 minutes in the microwave oven. After extractiveworkup (heptane-ethyl acetate, water) and chromatography, the titleproduct was obtained (0.15 g); 1H-NMR: 1.51 (2H), 2.01 (2H), 2.11 (6H),2.89 (3H), 3.06 (2H) , 7.78 (2H); 19F-NMR: −44.6; −63.7 ppm.

Example 45-(3-Aminopropyl)amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulfonylpyrazole(Compound number 4-03)

Triethylarnine (0.29 g, 2.9 mmol) was added to a mixture of5-bromo-1-(2,6-dichloro-4-trifluorormethylphenyl)-3-cyano-4-trifluoromethylsulfonylpyrazole(1.0 g, 1.9 mmol) and 1,3-diaminopropane (0.22 g, 2.9 mmol) intetrahydrofuran (10 ml). The mixture was stirred at 20-40° C. for 18hours. After extractive workup (heptane-ethyl acetate, water, sodiumhydroxide solution) the title product was obtained (0.74 g); 1 H-NMR:1.56 (2H), 2.86 and 3.02 (2H),;7.78 (2H); 19F-NMR: −63.7; −80.4 ppm.

The following Intermediate Example illustrates the preparation ofintermediates used in the synthesis of the above Examples.

Intermediate Example 15-[N-(3-Chloropropyl)N-methylamino]-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylthiopyrazole

1-Bromo-3-chloropropane (1.62 g, 1.6 mmol) was added to a mixture of1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-methylamino-4-trifluoromethylthiopyrazole(3.0 g, 6.9 mmol) and sodium hydride (0.35 g, 8.9 mmol) intetrahydrofuran (45 ml) under a nitrogen atmosphere, and the mixtureheated under reflux for 6 hours. After extractive workup (heptane-ethylacetate, water) and chromatography the title product was obtained as asolid (1.83 g); 1H-NMR: 1.81 (2H), 2.88 (3H), 3.21 (2H), 3.37 (2H), 7.80(2H); 19F-NMR: −44.8; −64.2 ppm.

The following preferred compounds shown in Tables 1 to 10 also form partof the present invention, and were or may be prepared in accordancewith, or analogously to, the above-mentioned Examples 1 to 4 or theabove-described general methods. Where subscripts are omitted they areintended, for example CH2 means CH₂. In the Tables Me means methyl, Etmeans ethyl, Pr means propyl, Bu means butyl, C5H11 means n-pentyl,C6H13 means n-hexyl, C2H4 means ethylene (—CH₂CH₂—), cC3H5 meanscyclopropyl, NHC3H6 means propyleneamino (—CH₂CH₂CH₂NH—), and Ph meansphenyl. In Table 9, N(C2H4SMe)C2H4 means a —CH₂CH₂N(CH₂CH₂SCH₃)-moiety.

19F-NMR spectra shift values are given in ppm.

Compound numbers are given for reference purposes only. TABLE 1Compounds of Formula (I) in which the substituents have the followingmeanings: R¹ is CN, W is C—Cl, R² is Cl, R³ is CF₃, R⁵ is CF₃ and A isCH₂ Compound number R⁴ NR⁶R⁷ n mp. ° C., NMR(ppm) 1-01 H NMe2 0 1-02 HNMe2 1 1-03 H NMe2 2 1-04 H NEt2 0 1-05 H NEt2 1 1-06 H NEt2 2 1-07 HNnPr2 0 1-09 H NnPr2 1 1-09 H NnPr2 2 1-10 H NnBu2 0 1-11 H NnBu2 1 1-12H NnBu2 2 1-13 H Nn(C5H11)2 0 1-14 H Nn(C5H11)2 1 1-15 H Nn(C5H11)2 21-16 H Nn(C6H13)2 0 1-17 H Nn(C6H13)2 1 1-18 H Nn(C6H13)2 2 1-19 HPyrrolidinyl 0 1-20 H Pyrrolidinyl 1 1-21 H Pyrrolidinyl 2 1-22 HPiperidinyl 0 1-23 H Piperidinyl 1 1-24 H Piperidinyl 2 1-25 HN-phthalimido 0 1-26 H N-phthalimido 1 19F: −63.8; −74.4 1-27 HN-phthalimido 2 1-28 Me NMe2 0 1-29 Me NMe2 1 1-30 Me NMe2 2 1-31 MeNEt2 0 1-32 Me NEt2 1 1-33 Me NEt2 2 1-34 Me NnPr2 0 1-35 Me NnPr2 11-36 Me NnPr2 2 1-37 Me NnBu2 0 1-38 Me NnBu2 1 1-39 Me NnBu2 2 1-40 MeNn(C5H11)2 0 1-41 Me Nn(C5H11)2 1 1-42 Me Nn(C5H11)2 2 1-43 MeNn(C6H13)2 0 1-44 Me Nn(C6H13)2 1 1-45 Me Nn(C6H13)2 2 1-46 MePyrrolidinyl 0 1-47 Me Pyrrolidinyl 1 1-48 Me Pyrrolidinyl 2 1-49 MePiperidinyl 0 1-50 Me Piperidinyl 1 1-51 Me Piperidinyl 2 1-52 MeN-phthalimido 0 1-53 Me N-phthalimido 1 19F: −63.8; −72.2 1-54 MeN-phthalimido 2

TABLE 2 Compounds of Formula (I) in which the substituents have thefollowing meanings: R¹ is CN, W is C—Cl, R² is Cl, R³ is CF₃, R⁵ is CF₃,R⁴ is H and A is CH₂CH₂ Compound number NR⁶R⁷ n mp. ° C., NMR(ppm) 2-01NH2 0 2-02 NH2 1 2-03 NH2 2 2-04 NHMe 0 2-05 NHMe 1 2-06 NHMe 2 2-07NHEt 0 2-09 NHEt 1 2-09 NHEt 2 2-10 NHnPr 0 2-11 NHnPr 1 2-12 NHnPr 22-13 NHnBu 0 2-14 NHnBu 1 2-15 NHnBu 2 2-16 NHnC5H11 0 2-17 NHnC5H11 12-18 NHnC5H11 2 2-19 NHnC6H13 0 2-20 NHnC6H13 1 2-21 NHnC6H13 2 2-22NHcC3H5 0 2-23 NHcC3H5 1 2-24 NHcC3H5 2 2-25 NHcC4H7 0 2-26 NHcC4H7 12-27 NHcC4H7 2 2-28 NHcC5H9 0 2-29 NHcC5H9 1 2-30 NHcC5H9 2 2-31NHcC6H11 0 2-32 NHcC6H11 1 2-33 NHcC6H11 2 2-34 NHCH2C6H5 0 2-35NHCH2C6H5 1 2-36 NHCH2C6H5 2 2-37 NHC2H4C6H5 0 2-38 NHC2H4C6H5 1 2-39NHC2H4C6H5 2 2-40 NHC6H5 0 2-41 NHC6H5 1 2-42 NHC6H5 2 2-43 NHCH2CH═CH20 2-44 NHCH2CH═CH2 1 2-45 NHCH2CH═CH2 2 2-46 NMe2 0 2-47 NMe2 1 2-48NMe2 2 2-49 NEt2 0 2-50 NEt2 1 19F: −64.2; −74.5 2-51 NEt2 2 19F: −64.2;−81.1 2-52 NEtMe 0 2-53 NEtMe 1 2-54 NEtMe 2 2-55 NnPr2 0 2-56 NnPr2 12-57 NnPr2 2 2-58 NnBu2 0 2-59 NnBu2 1 2-60 NnBu2 2 2-61 Nn(C5H11)2 02-62 Nn(C5H11)2 1 2-63 Nn(C5H11)2 2 2-64 Nn(C6H13)2 0 2-65 Nn(C6H13)2 12-66 Nn(C6H13)2 2 2-67 Pyrrolidinyl 0 2-68 Pyrrolidinyl 1 2-69Pyrrolidinyl 2 2-70 Piperidinyl 0 2-71 Piperidinyl 1 2-72 Piperidinyl 22-73 NMeCH2C6H5 0 2-74 NMeCH2C6H5 1 2-75 NMeCH2C6H5 2 2-76 NMeC2H4C6H5 02-77 NMeC2H4C6H5 1 2-78 NMeC2H4C6H5 2 2-79 Morpholinyl 0 2-80Morpholinyl 1 2-81 Morpholinyl 2 2-82 (4-Methyl-piperazin)-1-yl 0 2-83(4-Methyl-piperazin)-1-yl 1 2-84 (4-Methyl-piperazin)-1-yl 2 2-85(4-Acetyl-piperazin)-1-yl 0 2-86 (4-Acetyl-piperazin)-1-yl 1 2-87(4-Acetyl-piperazin)-1-yl 2 19F: −64.1; −81.2 2-88(4-Benzyl-piperazin)-1-yl 0 2-89 (4-Benzyl-piperazin)-1-yl 1 2-90(4-Benzyl-piperazin)-1-yl 2

TABLE 3 Compounds of Formula (I) in which the substituents have thefollowing meanings: R¹ is CN, W is C—Cl, R² is Cl, R³ is CF₃, R⁴ is Me,R⁵ is CF₃ and A is CH₂CH₂ Compound number NR⁶R⁷ n mp. ° C., NMR(ppm)3-01 NH2 0 3-02 NH2 1 3-03 NH2 2 3-04 NHMe 0 3-05 NHMe 1 3-06 NHMe 23-07 NHEt 0 3-09 NHEt 1 3-09 NHEt 2 3-10 NHnPr 0 3-11 NHnPr 1 3-12 NHnPr2 3-13 NHnBu 0 3-14 NHnBu 1 3-15 NHnBu 2 3-16 NHnC5H11 0 3-17 NHnC5H11 13-18 NHnC5H11 2 3-19 NHnC6H13 0 3-20 NHnC6H13 1 3-21 NHnC6H13 2 3-22NHcC3H5 0 3-23 NHcC3H5 1 3-24 NHcC3H5 2 3-25 NHcC4H7 0 3-26 NHcC4H7 13-27 NHcC4H7 2 3-28 NHcC5H9 0 3-29 NHcC5H9 1 3-30 NHcC5H9 2 3-31NHcC6H11 0 3-32 NHcC6H11 1 3-33 NHcC6H11 2 3-34 NHCH2C6H5 0 3-35NHCH2C6H5 1 3-36 NHCH2C6H5 2 3-37 NHC2H4C6H5 0 3-38 NHC2H4C6H5 1 3-39NHC2H4C6H5 2 3-40 NHC6H5 0 3-41 NHC6H5 1 3-42 NHC6H5 2 3-43 NHCH2CH═CH20 3-44 NHCH2CH═CH2 1 3-45 NHCH2CH═CH2 2 3-46 NMe2 0 3-47 NMe2 1 3-48NMe2 2 19F: −64.2; −79.2 3-49 NEt2 0 3-50 NEt2 1 19F: −64.2; −73.0 3-51NEt2 2 3-52 NEtMe 0 3-53 NEtMe 1 3-54 NEtMe 2 3-55 NnPr2 0 3-56 NnPr2 13-57 NnPr2 2 3-58 NnBu2 0 3-59 NnBu2 1 3-60 NnBu2 2 3-61 Nn(C5H11)2 03-62 Nn(C5H11)2 1 3-63 Nn(C5H11)2 2 3-64 Nn(C6H13)2 0 3-65 Nn(C6H13)2 13-66 Nn(C6H13)2 2 3-67 Pyrrolidinyl 0 3-68 Pyrrolidinyl 1 3-69Pyrrolidinyl 2 3-70 Piperidinyl 0 3-71 Piperidinyl 1 3-72 Piperidinyl 23-73 NMeCH2C6H5 0 3-74 NMeCH2C6H5 1 3-75 NMeCH2C6H5 2 3-76 NMeC2H4C6H5 03-77 NMeC2H4C6H5 1 3-78 NMeC2H4C6H5 2 3-79 Morpholinyl 0 3-80Morpholinyl 1 3-81 Morpholinyl 2 3-82 (4-Methyl-piperazin)-1-yl 0 3-83(4-Methyl-piperazin)-1-yl 1 3-84 (4-Methyl-piperazin)-1-yl 2 3-85(4-Acetyl-piperazin)-1-yl 0 3-86 (4-Acetyl-piperazin)-1-yl 1 3-87(4-Acetyl-piperazin)-1-yl 2 3-88 (4-Benzyl-piperazin)-1-yl 0 3-89(4-Benzyl-piperazin)-1-yl 1 3-90 (4-Benzyl-piperazin)-1-yl 2

TABLE 4 Compounds of Formula (I) in which the substituents have thefollowing meanings: R¹ is CN, W is C—Cl, R² is Cl, R³ is CF₃, R⁴ is H,R⁵ is CF₃ and A is CH₂CH₂CH₂ Compound number NR⁶R⁷ n mp. ° C., NMR(ppm)4-01 NH2 0 4-02 NH2 1 4-03 NH2 2 19F: −63.7; −80.4 4-04 NHMe 0 4-05 NHMe1 4-06 NHMe 2 4-07 NHEt 0 4-09 NHEt 1 4-09 NHEt 2 4-10 NHnPr 0 4-11NHnPr 1 4-12 NHnPr 2 4-13 NHnBu 0 4-14 NHnBu 1 4-15 NHnBu 2 4-16NHnC5H11 0 4-17 NHnC5H11 1 4-18 NHnC5H11 2 4-19 NHnC6H13 0 4-20 NHnC6H131 4-21 NHnC6H13 2 4-22 NHcC3H5 0 4-23 NHcC3H5 1 4-24 NHcC3H5 2 4-25NHcC4H7 0 4-26 NHcC4H7 1 4-27 NHcC4H7 2 4-28 NHcC5H9 0 4-29 NHcC5H9 14-30 NHcC5H9 2 4-31 NHcC6H11 0 4-32 NHcC6H11 1 4-33 NHcC6H11 2 4-34NHCH2C6H5 0 4-35 NHCH2C6H5 1 4-36 NHCH2C6H5 2 4-37 NHC2H4C6H5 0 4-38NHC2H4C6H5 1 4-39 NHC2H4C6H5 2 4-40 NHC6H5 0 4-41 NHC6H5 1 4-42 NHC6H5 24-43 NHCH2CH═CH2 0 4-44 NHCH2CH═CH2 1 4-45 NHCH2CH═CH2 2 4-46 NMe2 04-47 NMe2 1 4-48 NMe2 2 4-49 NEt2 0 4-50 NEt2 1 4-51 NEt2 2 19F: −64.2;−80.9 4-52 NEtMe 0 4-53 NEtMe 1 4-54 NEtMe 2 4-55 NnPr2 0 4-56 NnPr2 14-57 NnPr2 2 4-58 NnBu2 0 4-59 NnBu2 1 4-60 NnBu2 2 4-61 Nn(C5H11)2 04-62 Nn(C5H11)2 1 4-63 Nn(C5H11)2 2 4-64 Nn(C6H13)2 0 4-65 Nn(C6H13)2 14-66 Nn(C6H13)2 2 4-67 Pyrrolidinyl 0 4-68 Pyrrolidinyl 1 4-69Pyrrolidinyl 2 4-70 Piperidinyl 0 4-71 Piperidinyl 1 4-72 Piperidinyl 24-73 NMeCH2C6H5 0 4-74 NMeCH2C6H5 1 4-75 NMeCH2C6H5 2 4-76 NMeC2H4C6H5 04-77 NMeC2H4C6H5 1 4-78 NMeC2H4C6H5 2 4-79 Morpholinyl 0 4-80Morpholinyl 1 4-81 Morpholinyl 2 4-82 (4-Methyl-piperazin)-1-yl 0 4-83(4-Methyl-piperazin)-1-yl 1 4-84 (4-Methyl-piperazin)-1-yl 2 4-85(4-Acetyl-piperazin)-1-yl 0 4-86 (4-Acetyl-piperazin)-1-yl 1 4-87(4-Acetyl-piperazin)-1-yl 2 4-88 (4-Benzyl-piperazin)-1-yl 0 4-89(4-Benzyl-piperazin)-1-yl 1 4-90 (4-Benzyl-piperazin)-1-yl 2

TABLE 5 Compounds of Formula (I) in which the substituents have thefollowing meanings: R¹ is CN, W is C—Cl, R² is Cl, R³ is CF₃, R⁴ is Me,R⁵ is CF₃ and A is CH₂CH₂CH₂ Compound number NR⁶R⁷ n mp. ° C., NMR(ppm)5-01 NH2 0 5-02 NH2 1 5-03 NH2 2 5-04 NHMe 0 5-05 NHMe 1 5-06 NHMe 25-07 NHEt 0 5-09 NHEt 1 5-09 NHEt 2 5-10 NHnPr 0 5-11 NHnPr 1 5-12 NHnPr2 5-13 NHnBu 0 19F: −44.9; −64.1 5-14 NHnBu 1 5-15 NHnBu 2 5-16 NHnC5H110 5-17 NHnC5H11 1 5-18 NHnC5H11 2 5-19 NHnC6H13 0 5-20 NHnC6H13 1 5-21NHnC6H13 2 5-22 NHcC3H5 0 5-23 NHcC3H5 1 5-24 NHcC3H5 2 5-25 NHcC4H7 05-26 NHcC4H7 1 5-27 NHcC4H7 2 5-28 NHcC5H9 0 5-29 NHcC5H9 1 5-30 NHcC5H92 5-31 NHcC6H11 0 5-32 NHcC6H11 1 5-33 NHcC6H11 2 5-34 NHCH2C6H5 0 5-35NHCH2C6H5 1 5-36 NHCH2C6H5 2 5-37 NHC2H4C6H5 0 5-38 NHC2H4C6H5 1 5-39NHC2H4C6H5 2 5-40 NHC6H5 0 5-41 NHC6H5 1 5-42 NHC6H5 2 5-43 NHCH2CH═CH20 5-44 NHCH2CH═CH2 1 5-45 NHCH2CH═CH2 2 5-46 NMe2 0 19F: −44.6; −63.75-47 NMe2 1 5-48 NMe2 2 5-49 NEt2 0 19F: −44.7; −63.7 5-50 NEt2 1 19F:−64.2; −73.2 5-51 NEt2 2 (a) 5-52 NEtMe 0 mp. 70 5-53 NEtMe 1 5-54 NEtMe2 5-55 NnPr2 0 19F: −45.9; −64.1 5-56 NnPr2 1 5-57 NnPr2 2 5-58 NnBu2 05-59 NnBu2 1 5-60 NnBu2 2 5-61 Nn(C5H11)2 0 5-62 Nn(C5H11)2 1 5-63Nn(C5H11)2 2 5-64 Nn(C6H13)2 0 5-65 Nn(C6H13)2 1 5-66 Nn(C6H13)2 2 5-67Pyrrolidinyl 0 19F: −44.6; −63.7 5-68 Pyrrolidinyl 1 5-69 Pyrrolidinyl 25-70 Piperidinyl 0 19F: −44.9; −64.1 5-71 Piperidinyl 1 5-72 Piperidinyl2 5-73 NMeCH2C6H5 0 19F: −44.7; −63.7 5-74 NMeCH2C6H5 1 5-75 NMeCH2C6H52 5-76 NMeC2H4C6H5 0 5-77 NMeC2H4C6H5 1 5-78 NMeC2H4C6H5 2 5-79Morpholinyl 0 19F: −44.9; −64.1 5-80 Morpholinyl 1 5-81 Morpholinyl 25-82 (4-Methyl-piperazin)-1-yl 0 5-83 (4-Methyl-piperazin)-1-yl 1 5-84(4-Methyl-piperazin)-1-yl 2 5-85 (4-Acetyl-piperazin)-1-yl 0 5-86(4-Acetyl-piperazin)-1-yl 1 5-87 (4-Acetyl-piperazin)-1-yl 2 5-88(4-Benzyl-piperazin)-1-yl 0 5-89 (4-Benzyl-piperazin)-1-yl 1 5-90(4-Benzyl-piperazin)-1-yl 2Note:(a) trifluoroacetic acid salt

TABLE 6 Compounds of Formula (I) in which the substituents have thefollowing meanings: R¹ is CN, W is C—Cl, R² is Cl, R³ is CF₃, R⁴ is H,R⁵ is CF₃ and A is CH₂CH₂CH₂CH₂ Compound number NR⁶R⁷ n mp. ° C.,NMR(ppm) 6-01 NH2 0 6-02 NH2 1 6-03 NH2 2 19F: −63.7; −80.4 6-04 NHMe 06-05 NHMe 1 6-06 NHMe 2 6-07 NHEt 0 6-09 NHEt 1 6-09 NHEt 2 6-10 NHnPr 06-11 NHnPr 1 6-12 NHnPr 2 6-13 NHnBu 0 6-14 NHnBu 1 6-15 NHnBu 2 6-16NHnC5H11 0 6-17 NHnC5H11 1 6-18 NHnC5H11 2 6-19 NHnC6H13 0 6-20 NHnC6H131 6-21 NHnC6H13 2 6-22 NHcC3H5 0 6-23 NHcC3H5 1 6-24 NHcC3H5 2 6-25NHcC4H7 0 6-26 NHcC4H7 1 6-27 NHcC4H7 2 6-28 NHcC5H9 0 6-29 NHcC5H9 16-30 NHcC5H9 2 6-31 NHcC6H11 0 6-32 NHcC6H11 1 6-33 NHcC6H11 2 6-34NHCH2C6H5 0 6-35 NHCH2C6H5 1 6-36 NHCH2C6H5 2 6-37 NHC2H4C6H5 0 6-38NHC2H4C6H5 1 6-39 NHC2H4C6H5 2 6-40 NHC6H5 0 6-41 NHC6H5 1 6-42 NHC6H5 26-43 NHCH2CH═CH2 0 6-44 NHCH2CH═CH2 1 6-45 NHCH2CH═CH2 2 6-46 NMe2 06-47 NMe2 1 6-48 NMe2 2 6-49 NEt2 0 6-50 NEt2 1 6-51 NEt2 2 6-52 NEtMe 06-53 NEtMe 1 6-54 NEtMe 2 6-55 NnPr2 0 6-56 NnPr2 1 6-57 NnPr2 2 6-58NnBu2 0 6-59 NnBu2 1 6-60 NnBu2 2 6-61 Nn(C5H11)2 0 6-62 Nn(C5H11)2 16-63 Nn(C5H11)2 2 6-64 Nn(C6H13)2 0 6-65 Nn(C6H13)2 1 6-66 Nn(C6H13)2 26-67 Pyrrolidinyl 0 6-68 Pyrrolidinyl 1 6-69 Pyrrolidinyl 2 6-70Piperidinyl 0 6-71 Piperidinyl 1 6-72 Piperidinyl 2 6-73 NMeCH2C6H5 06-74 NMeCH2C6H5 1 6-75 NMeCH2C6H5 2 6-76 NMeC2H4C6H5 0 6-77 NMeC2H4C6H51 6-78 NMeC2H4C6H5 2 6-79 Morpholinyl 0 6-80 Morpholinyl 1 6-81Morpholinyl 2 6-82 (4-Methyl-piperazin)-1-yl 0 6-83(4-Methyl-piperazin)-1-yl 1 6-84 (4-Methyl-piperazin)-1-yl 2 6-85(4-Acetyl-piperazin)-1-yl 0 6-86 (4-Acetyl-piperazin)-1-yl 1 6-87(4-Acetyl-piperazin)-1-yl 2 6-88 (4-Benzyl-piperazin)-1-yl 0 6-89(4-Benzyl-piperazin)-1-yl 1 6-90 (4-Benzyl-piperazin)-1-yl 2

TABLE 7 Compounds of Formula (I) in which the substituents have thefollowing meanings: R¹ is CN, W is C—Cl, R² is Cl, R³ is CF₃, R⁴ is Me,R⁵ is CF₃ and A is CH₂CH₂CH₂CH₂ Compound number NR⁶R⁷ n mp. ° C.,NMR(ppm) 7-01 NH2 0 7-02 NH2 1 7-03 NH2 2 7-04 NHMe 0 7-05 NHMe 1 7-06NHMe 2 7-07 NHEt 0 7-09 NHEt 1 7-09 NHEt 2 7-10 NHnPr 0 7-11 NHnPr 17-12 NHnPr 2 7-13 NHnBu 0 7-14 NHnBu 1 7-15 NHnBu 2 7-16 NHnC5H11 0 7-17NHnC5H11 1 7-18 NHnC5H11 2 7-19 NHnC6H13 0 7-20 NHnC6H13 1 7-21 NHnC6H132 7-22 NHcC3H5 0 7-23 NHcC3H5 1 7-24 NHcC3H5 2 7-25 NHcC4H7 0 7-26NHcC4H7 1 7-27 NHcC4H7 2 7-28 NHcC5H9 0 7-29 NHcC5H9 1 7-30 NHcC5H9 27-31 NHcC6H11 0 7-32 NHcC6H11 1 7-33 NHcC6H11 2 7-34 NHCH2C6H5 0 7-35NHCH2C6H5 1 7-36 NHCH2C6H5 2 7-37 NHC2H4C6H5 0 7-38 NHC2H4C6H5 1 7-39NHC2H4C6H5 2 7-40 NHC6H5 0 7-41 NHC6H5 1 7-42 NHC6H5 2 7-43 NHCH2CH═CH20 7-44 NHCH2CH═CH2 1 7-45 NHCH2CH═CH2 2 7-46 NMe2 0 7-47 NMe2 1 7-48NMe2 2 7-49 NEt2 0 7-50 NEt2 1 7-51 NEt2 2 7-52 NEtMe 0 7-53 NEtMe 17-54 NEtMe 2 7-55 NnPr2 0 7-56 NnPr2 1 7-57 NnPr2 2 7-58 NnBu2 0 7-59NnBu2 1 7-60 NnBu2 2 7-61 Nn(C5H11)2 0 7-62 Nn(C5H11)2 1 7-63 Nn(C5H11)22 7-64 Nn(C6H13)2 0 7-65 Nn(C6H13)2 1 7-66 Nn(C6H13)2 2 7-67Pyrrolidinyl 0 7-68 Pyrrolidinyl 1 7-69 Pyrrolidinyl 2 7-70 Piperidinyl0 7-71 Piperidinyl 1 7-72 Piperidinyl 2 7-73 NMeCH2C6H5 0 7-74NMeCH2C6H5 1 7-75 NMeCH2C6H5 2 7-76 NMeC2H4C6H5 0 7-77 NMeC2H4C6H5 17-78 NMeC2H4C6H5 2 7-79 Morpholinyl 0 7-80 Morpholinyl 1 7-81Morpholinyl 2 7-82 (4-Methyl-piperazin)-1-yl 0 7-83(4-Methyl-piperazin)-1-yl 1 7-84 (4-Methyl-piperazin)-1-yl 2 7-85(4-Acetyl-piperazin)-1-yl 0 7-86 (4-Acetyl-piperazin)-1-yl 1 7-87(4-Acetyl-piperazin)-1-yl 2 7-88 (4-Benzyl-piperazin)-1-yl 0 7-89(4-Benzyl-piperazin)-1-yl 1 7-90 (4-Benzyl-piperazin)-1-yl 2

TABLE 8 Compounds of Formula (I) in which the substituents have thefollowing meanings: R¹ is CN, W is C—Cl, R² is Cl, R³ is CF₃ and R⁵ isCF₃ Compound mp. ° C., number NR⁴-A NR⁶R⁷ n NMR(ppm) 8-01 NHC2H4NH—COCH3 0 8-02 NHC2H4 NH—COCH3 1 8-03 NHC2H4 NH—COCH3 2 8-04 NMeC2H4NH—COCH3 0 8-05 NMeC2H4 NH—COCH3 1 8-06 NMeC2H4 NH—COCH3 2 8-07 NHC3H6NH—COCH3 0 8-09 NHC3H6 NH—COCH3 1 8-09 NHC3H6 NH—COCH3 2 8-10 NMeC3H6NH—COCH3 0 8-11 NMeC3H6 NH—COCH3 1 8-12 NMeC3H6 NH—COCH3 2 8-13 NHC4H8NH—COCH3 0 8-14 NHC4H8 NH—COCH3 1 8-15 NHC4H8 NH—COCH3 2 19F: −64.2;−81.0 8-16 NMeC4H8 NH—COCH3 0 8-17 NMeC4H8 NH—COCH3 1 8-18 NMeC4H8NH—COCH3 2 8-19 NHC2H4 NMe—COCH3 0 8-20 NHC2H4 NMe—COCH3 1 8-21 NHC2H4NMe—COCH3 2 8-22 NMeC2H4 NMe—COCH3 0 8-23 NMeC2H4 NMe—COCH3 1 8-24NMeC2H4 NMe—COCH3 2 8-25 NHC3H6 NMe—COCH3 0 8-26 NHC3H6 NMe—COCH3 1 8-27NHC3H6 NMe—COCH3 2 8-28 NMeC3H6 NMe—COCH3 0 8-29 NMeC3H6 NMe—COCH3 18-30 NMeC3H6 NMe—COCH3 2 8-31 NHC4H8 NMe—COCH3 0 8-32 NHC4H8 NMe—COCH3 18-33 NHC4H8 NMe—COCH3 2 8-34 NMeC4H8 NMe—COCH3 0 8-35 NMeC4H8 NMe—COCH31 8-36 NMeC4H8 NMe—COCH3 2 8-37 NHC2H4 N-phthalimido 0 8-38 NHC2H4N-phthalimido 1 8-39 NHC2H4 N-phthalimido 2 8-40 NMeC2H4 N-phthalimido 08-41 NMeC2H4 N-phthalimido 1 8-42 NMeC2H4 N-phthalimido 2 8-43 NHC3H6N-phthalimido 0 8-44 NHC3H6 N-phthalimido 1 8-45 NHC3H6 N-phthalimido 28-46 NMeC3H6 N-phthalimido 0 8-47 NMeC3H6 N-phthalimido 1 19F: −64.1;−73.2 8-48 NMeC3H6 N-phthalimido 2 8-49 NHC4H8 N-phthalimido 0 8-50NHC4H8 N-phthalimido 1 8-51 NHC4H8 N-phthalimido 2 8-52 NMeC4H8N-phthalimido 0 8-53 NMeC4H8 N-phthalimido 1 8-54 NMeC4H8 N-phthalimido2 8-55 NHC2H4 2-Oxopyrrolidinyl 0 8-56 NHC2H4 2-Oxopyrrolidinyl 1 8-57NHC2H4 2-Oxopyrrolidinyl 2 8-58 NMeC2H4 2-Oxopyrrolidinyl 0 8-59 NMeC2H42-Oxopyrrolidinyl 1 8-60 NMeC2H4 2-Oxopyrrolidinyl 2 8-61 NHC3H62-Oxopyrrolidinyl 0 8-62 NHC3H6 2-Oxopyrrolidinyl 1 8-63 NHC3H62-Oxopyrrolidinyl 2 19F: −63.8; −80.1 8-64 NMeC3H6 2-Oxopyrrolidinyl 08-65 NMeC3H6 2-Oxopyrrolidinyl 1 8-66 NMeC3H6 2-Oxopyrrolidinyl 2 8-67NHC4H8 2-Oxopyrrolidinyl 0 8-68 NHC4H8 2-Oxopyrrolidinyl 1 8-69 NHC4H82-Oxopyrrolidinyl 2 8-70 NMeC4H8 2-Oxopyrrolidinyl 0 8-71 NMeC4H82-Oxopyrrolidinyl 1 8-72 NMeC4H8 2-Oxopyrrolidinyl 2 8-73 NHC2H42-Oxopiperidinyl 0 8-74 NHC2H4 2-Oxopiperidinyl 1 8-75 NHC2H42-Oxopiperidinyl 2 8-76 NMeC2H4 2-Oxopiperidinyl 0 8-77 NMeC2H42-Oxopiperidinyl 1 8-78 NMeC2H4 2-Oxopiperidinyl 2 8-79 NHC3H62-Oxopiperidinyl 0 8-80 NHC3H6 2-Oxopiperidinyl 1 8-81 NHC3H62-Oxopiperidinyl 2 8-82 NMeC3H6 2-Oxopiperidinyl 0 8-83 NMeC3H62-Oxopiperidinyl 1 8-84 NMeC3H6 2-Oxopiperidinyl 2 8-85 NHC4H82-Oxopiperidinyl 0 8-86 NHC4H8 2-Oxopiperidinyl 1 8-87 NHC4H82-Oxopiperidinyl 2 8-88 NMeC4H8 2-Oxopiperidinyl 0 8-89 NMeC4H82-Oxopiperidinyl 1 8-90 NMeC4H8 2-Oxopiperidinyl 2

TABLE 9 Compounds of Formula (I) in which the substituents have thefollowing meanings: R¹ is CN, W is C—Cl, R² is Cl, R³ is CF₃ and R⁵ isCF₃ Compound number NR⁴-A NR⁶R⁷ n mp. ° C., NMR(ppm) 9-01 N(COCH3)C2H4NMe2 0 9-02 N(COCH3)C2H4 NMe2 1 9-03 N(COCH3)C2H4 NMe2 2 9-04N(COCH3)C2H4 NEt2 0 9-05 N(COCH3)C2H4 NEt2 1 9-06 N(COCH3)C2H4 NEt2 29-07 N(COCH3)C2H4 NEtMe 0 9-09 N(COCH3)C2H4 NEtMe 1 9-09 N(COCH3)C2H4NEtMe 2 9-10 N(COCH3)C3H6 NMe2 0 9-11 N(COCH3)C3H6 NMe2 1 9-12N(COCH3)C3H6 NMe2 2 9-13 N(COCH3)C3H6 NEt2 0 9-14 N(COCH3)C3H6 NEt2 19-15 N(COCH3)C3H6 NEt2 2 9-16 N(COCH3)C3H6 NEtMe 0 9-17 N(COCH3)C3H6NEtMe 1 9-18 N(COCH3)C3H6 NEtMe 2 9-19 N(COOMe)C2H4 NMe2 0 9-20N(COOMe)C2H4 NMe2 1 9-21 N(COOMe)C2H4 NMe2 2 9-22 N(COOMe)C2H4 NEt2 09-23 N(COOMe)C2H4 NEt2 1 9-24 N(COOMe)C2H4 NEt2 2 9-25 N(COOMe)C2H4NEtMe 0 9-26 N(COOMe)C2H4 NEtMe 1 9-27 N(COOMe)C2H4 NEtMe 2 9-28N(COOMe)C3H6 NMe2 0 9-29 N(COOMe)C3H6 NMe2 1 9-30 N(COOMe)C3H6 NMe2 29-31 N(COOMe)C3H6 NEt2 0 9-32 N(COOMe)C3H6 NEt2 1 9-33 N(COOMe)C3H6 NEt22 9-34 N(COOMe)C3H6 NEtMe 0 9-35 N(COOMe)C3H6 NEtMe 1 9-36 N(COOMe)C3H6NEtMe 2 9-37 N(COOEt)C2H4 NMe2 0 9-38 N(COOEt)C2H4 NMe2 1 9-39N(COOEt)C2H4 NMe2 2 9-40 N(COOEt)C2H4 NEt2 0 9-41 N(COOEt)C2H4 NEt2 19-42 N(COOEt)C2H4 NEt2 2 19F: −64.0; −77.6;(a) 9-43 N(COOEt)C2H4 NEtMe 09-44 N(COOEt)C2H4 NEtMe 1 9-45 N(COOEt)C2H4 NEtMe 2 9-46 N(COOEt)C3H6NMe2 0 9-47 N(COOEt)C3H6 NMe2 1 9-48 N(COOEt)C3H6 NMe2 2 9-49N(COOEt)C3H6 NEt2 0 9-50 N(COOEt)C3H6 NEt2 1 9-51 N(COOEt)C3H6 NEt2 29-52 N(COOEt)C3H6 NEtMe 0 9-53 N(COOEt)C3H6 NEtMe 1 9-54 N(COOEt)C3H6NEtMe 2 9-55 N(C2H4SMe)C2H4 NMe2 0 9-56 N(C2H4SMe)C2H4 NMe2 1 9-57N(C2H4SMe)C2H4 NMe2 2 9-58 N(C2H4SMe)C2H4 NEt2 0 9-59 N(C2H4SMe)C2H4NEt2 1 9-60 N(C2H4SMe)C2H4 NEt2 2 19F: −63.7; −78.3 9-61 N(C2H4SMe)C2H4NEtMe 0 9-62 N(C2H4SMe)C2H4 NEtMe 1 9-63 N(C2H4SMe)C2H4 NEtMe 2 9-64N(C2H4SMe)C3H6 NMe2 0 9-65 N(C2H4SMe)C3H6 NMe2 1 9-66 N(C2H4SMe)C3H6NMe2 2 9-67 N(C2H4SMe)C3H6 NEt2 0 9-68 N(C2H4SMe)C3H6 NEt2 1 9-69N(C2H4SMe)C3H6 NEt2 2 19F: −63.7; −78.3 9-70 N(C2H4SMe)C3H6 NEtMe 0 9-71N(C2H4SMe)C3H6 NEtMe 1 9-72 N(C2H4SMe)C3H6 NEtMe 2Note(a) trifluoroacetic acid salt

TABLE 10 Compounds of Formula (I) in which the substituents have thefollowing meanings: R¹ is CN, W is C—Cl, R² is Cl, R³ is CF₃ and R⁵ isCF₃ Compound number N(R⁴)-A-NR⁶R⁷ n mp. ° C., NMR(ppm) 10-01(2,2,6,6-Tetramethylpiperidin-4-yl)amino 0 10-02(2,2,6,6-Tetramethylpiperidin-4-yl)amino 1 10-03(2,2,6,6-Tetramethylpiperidin-4-yl)amino 2 19F: −64.0; −80.4 10-04Piperidin-4-ylamino 0 10-05 Piperidin-4-ylamino 1 10-06Piperidin-4-ylamino 2 10-07 (1-Benzylpiperidin-4-yl)amino 0 10-09(1-Benzylpiperidin-4-yl)amino 1 10-09 (1-Benzylpiperidin-4-yl)amino 210-10 (1-Methylpiperidin-4-yl)amino 0 10-11(1-Methylpiperidin-4-yl)amino 1 10-12 (1-Methylpiperidin-4-yl)amino 210-13 (1-Benzylpiperidin-3-yl)amino 0 10-14(1-Benzylpiperidin-3-yl)amino 1 10-15 (1-Benzylpiperidin-3-yl)amino 210-16 Pyrrolidin-3-ylamino 0 10-17 Pyrrolidin-3-ylamino 1 10-18Pyrrolidin-3-ylamino 2 10-19 (1-Acetyl-piperidin-4-yl)amino 0 10-20(1-Acetyl-piperidin-4-yl)amino 1 10-21 (1-Acetyl-piperidin-4-yl)amino 210-22 (1-Methoxycarbonyl-piperidin-4-yl)amino 0 10-23(1-Methoxycarbonyl-piperidin-4-yl)amino 1 10-24(1-Methoxycarbonyl-piperidin-4-yl)amino 2 10-25(1-Ethoxycarbonyl-piperidin-4-yl)amino 0 10-26(1-Ethoxycarbonyl-piperidin-4-yl)amino 1 10-27(1-Ethoxycarbonyl-piperidin-4-yl)amino 2 10-28N-(1-Benzylpiperidin-4-yl)-N-methylamino 0 10-29N-(1-Benzylpiperidin-4-yl)-N-methylamino 1 10-30N-(1-Benzylpiperidin-4-yl)-N-methylamino 2 10-31N-(1-Methylpiperidin-4-yl)-N-methylamino 0 10-32N-(1-Methylpiperidin-4-yl)-N-methylamino 1 10-33N-(1-Methylpiperidin-4-yl)-N-methylamino 2 10-34N-(1-Benzylpiperidin-3-yl)-N-methylamino 0 10-35N-(1-Benzylpiperidin-3-yl)-N-methylamino 1 10-36N-(1-Benzylpiperidin-3-yl)-N-methylamino 2

According to a further feature of the present invention there isprovided a method for the control of pests at a locus which comprisesapplying thereto an effective amount of a compound of formula (I) or asalt thereof. For this purpose, the said compound is normally used inthe form of a pesticidal composition (i.e. in association withcompatible diluents or carriers and/or surface active agents suitablefor use in pesticidal compositions), for example as hereinafterdescribed.

The term “compound of the invention” as used hereinafter embraces a5-aminoalkylaminopyrazole derivative of formula (I) as defined above anda pesticidally acceptable salt thereof.

One aspect of the present invention as defined above is a method for thecontrol of pests at a locus. The locus includes, for example, the pestitself, the place (plant, field, forest, orchard, waterway, soil, plantproduct, or the like) where the pest resides or feeds, or a placesusceptible topfuture infestation by the pest. The compound of theinvention may therefore be applied, directly to the pest, to the placewhere the pest resides or feeds, or to the place susceptible to futureinfestation by the pest. As is evident from the foregoing pesticidaluses, the present invention provides pesticidally active compounds andmethods of use of said compounds for the control of a number of pestspecies which includes: arthropods, especially insects or mites, orplant nematodes. The compound of the invention may thus beadvantageously employed in practical uses, for example, in agriculturalor horticultural crops, in forestry, in veterinary medicine or livestockhusbandry, or in public health. The compounds of the invention may beused for example in the following applications and on the followingpests:

For the control of soil insects, such as corn rootworm, termites(especially for protection of structures), root maggots, wireworms, rootweevils, stalkborers, cutworms, root aphids, or grubs. They may also beused to provide activity against plant pathogenic nematodes, such asroot-knot, cyst, dagger, lesion, or stem or bulb nematodes, or againstmites. For the control of soil pests, for example corn rootworm, thecompounds are advantageously applied to or incorporated at an effectiverate into the soil in which crops are planted or to be planted or to theseeds or growing plant roots.

In the area of public health, the compounds are especially useful in thecontrol of many insects, especially filth flies or other Dipteran pests,such as houseflies, stableflies, soldierflies, homflies, deerflies,horseflies, midges, punkies, blackflies, or mosquitoes.

In the protection of stored products, for example cereals, includinggrain or flour, groundnuts, animal feedstuffs, timber or householdgoods, e.g. carpets and textiles, compounds of the invention are usefulagainst attack by arthropods, more especially beetles, includingweevils, moths or mites, for example Ephestia spp. (flour moths),Anthrenus spp. (carpet beetles), Tribolium spp. (flour beetles),Sitophilus spp. (grain weevils) or Acarus spp. (mites).

In the control of cockroaches, ants or termites or similar arthropodpests in infested domestic or industrial premises or in the control ofmosquito larvae in waterways, wells, reservoirs or other running orstanding water.

For the treatment of.foundations, structures or soil in the preventionof the attack on building by termites, for example, Reticulitermes spp.,Heterotermes spp., Coptotermes spp.

In agriculture against adults, larvae and eggs of Lepidoptera(butterflies and moths), e.g. Heliothis spp. such as Heliothis virescens(tobacco budworm), Heliothis armigera and Heliothis zea. Against adultsand larvae of Coleoptera (beetles) e.g. Anthonomus spp. e.g. grandis(cotton boll weevil), Leptinotarsa decemlineata (Colorado potatobeetle), Diabrotica spp. (corn rootworms). Against Heteroptera(Hemiptera and Homoptera) e.g. Psylla spp., Bemisia spp., Trialeurodesspp., Aphis spp., Myzus spp., Megoura viciae, Phylloxera spp.,Nephotettix spp. (rice leaf hoppers), Nilaparvata spp.

Against Diptera e.g. Musca spp. Against Thysanoptera such as Thripstabaci.

Against Orthoptera such as Locusta and Schistocerca spp., (locusts andcrickets) e.g. Gryllus spp., and Acheta spp. for example, Blattaorientalis, Periplanieta americana, Blatella germanica, Locustamigratoria migratorioides, and Schistocerca gregaria. Against Collembolae.g. Periplaneta spp. and Blatella spp. (roaches).

Against arthropods of agricultural significance such as Acari (mites)e.g. Tetranychus spp., and Panonychus spp.

Against nematodes which attack plants or trees of importance toagriculture, forestry or horticulture either directly or by spreadingbacterial, viral, mycoplasma or fungal diseases of the plants. Forexample root-knot nematodes such as Meloidogyne spp. (e.g. M.incognita).

In the field of veterinary medicine or livestock husbandry or in themaintenance of public health against arthropods which are parasiticinternally or externally upon vertebrates, particularly warm-bloodedvertebrates, for example domestic animals, e.g. cattle, sheep, goats,equines, swine, poultry, dogs or cats, for example Acarina, includingticks (e.g. soft-bodied-ticks including Argasidae spp. e.g. Argas spp.and Ornithodorus spp. (e.g. Ornithodorus moubata); hard-bodied ticksincluding Ixodidae spp., e.g. Boophilus spp. e.g. Boophilus microplus,Rhipicephalus spp. e.g. Rhipicephalus appendiculatus and Rhipicephalussanguineus; mites (e.g. Damalinia spp.); fleas (e.g. Ctenocephalidesspp. e.g. Ctenocephalides felis (cat flea) and Ctenocephalides canis(dog flea)); lice e.g. Menopon spp.; Diptera (e.g. Aedes spp., Anophelesspp., Musca spp., Hypoderma spp.); Hemiptera.; Dictyoptera (e.g.Periplaneta spp., Blatella spp.); Hymenoptera; for example againstinfections of the gastro-intestinal tract caused by parasitic nematodeworms, for example members of the family Trichostrongylidae.

In a preferred aspect of the invention the compounds of formula (I) areused for the control of parasites of animals. Preferably the animal tobe treated is a domestic companion animal such as a dog or a cat.

In a further aspect of the invention the compounds of formula (I) orsalts or compositions thereof are used for the preparation of aveterinary medicament.

A further feature of the invention thus relates to the use of a compoundof formula (I) or a salt thereof, or of a composition thereof, for thecontrol of pests.

In practical use for the control of arthropods, especially insects ormites, or helminths, especially nematode pests of plants, a method, forexample, comprises applying to the plants or to the medium in which theygrow an effective amount of a compound of the invention. For such amethod, the compound of the invention is generally applied to the locusin which the arthropod or nematode infestation is to be controlled at aneffective rate in the range of about 2 g to about 1 kg of the activecompound per hectare of locus treated. Under ideal conditions, dependingon the pest to be controlled, a lower rate may offer adequateprotection. On the other hand, adverse weather conditions, resistance ofthe pest or other factors may require that the active ingredient be usedat higher rates. The optimum rate depends usually upon a number offactors, for example, the type of pest being controlled, the type or thegrowth stage of the infested plant, the row spacing or also the methodof application. Preferably an effective rate range of the activecompound is from about 10 g/ha to about 400 g/ha, more preferably fromabout 50 g/ha to about 200 g/ha. When a pest is soil-borne, the activecompound generally in a formulated composition, is distributed evenlyover the area to be treated (ie, for example broadcast or bandtreatment) in any convenient manner and is applied at rates from about10 g/ha to about 400 g ai/ha, preferably from about 50 g/ha to about 200g ai/ha. When applied as a root dip to seedlings or drip irrigation toplants the liquid solution or suspension contains from about 0.075 toabout 1000 mg ai/l, preferably from about 25 to about 200 mg ai/l.Application may be made, if desired, to the field or crop-growing areagenerally or in close proximity to the seed or plant to be protectedfrom attack. The compound of the invention can be washed into the soilby spraying with water over the area or can be left to the naturalaction of rainfall. During or after application, the formulated compoundcan, if desired, be distributed mechanically in the soil, for example byploughing, disking, or use of drag chains. Application can be prior toplanting, at planting, after planting but before sprouting has takenplace, or after sprouting.

The compound of the invention and methods of control of pests therewithare of particular value in the protection of field, forage, plantation,glasshouse, orchard or vineyard crops, of ornamentals, or of plantationor forest trees, for example: cereals (such as wheat or rice), cotton,vegetables (such as peppers), field crops (such as sugar beets, soybeansor oil seed rape), grassland or forage crops (such as maize or sorghum),orchards or groves (such as of stone or pit fruit or citrus), ornamentalplants, flowers or vegetables or shrubs under glass or in gardens orparks, or forest trees (both deciduous and evergreen) in forests,plantations or nurseries. They are also valuable in the protection oftimber (standing, felled, converted, stored or structural) from attack,for example, by sawflies or beetles or termites. They have applicationsin the protection of stored products such as grains, fruits, nuts,spices or tobacco, whether whole, milled or compounded into products,from moth, beetle, mite or grain weevil attack. Also protected arestored animal products such as skins, hair, wool or feathers in naturalor converted form (e.g. as carpets or textiles) from moth or beetleattack as well as stored meat, fish or grains from beetle, mite or flyattack.

Additionally, the compound of the invention and methods of use thereofare of particular value in the control of arthropods or helminths whichare injurious to, or spread or act as vectors of diseases domesticanimals, for example those hereinbefore mentioned, and more especiallyin the control of ticks, mites, lice, fleas, midges, or biting, nuisanceor myiasis flies. The compounds of the invention are particularly usefulin controlling arthropods or helminths which are present inside domestichost animals or which feed in or on the skin or suck the blood of theanimal, for which purpose they may be administered orally, parenterally,percutaneously or topically.

The compositions hereinafter described for application to growing cropsor crop growing loci or as a seed dressing may, in general,alternatively be employed in the protection of stored products,household goods, property or areas of the general environment. Suitablemeans of applying the compounds of the invention include: to growingcrops as foliar sprays (for example as an in-furrow spray), dusts,granules, fogs or foams or also as suspensions of finely divided orencapsulated compositions as soil or root treatments by liquid drenches,dusts, granules, smokes or foams; to seeds of crops via application asseed dressings, e.g. by liquid slurries or dusts;

to animals infested by or exposed to infestation by arthropods orhelminths, by parenteral, oral or topical application of compositions inwhich the active ingredient exhibits an immediate and/or prolongedaction over a period of time against the arthropods or helminths, forexample by incorporati on in feed or suitable orally-ingestiblepharmaceutical formulations, edible baits, salt licks, dietarysupplements, pour-on formulations, sprays, baths, dips, showers, jets,dusts, greases, shampoos, creams, wax smears or livestock self-treatmentsystems;

to the environment in general or to specific location s where pests maylurk, including stored products, timber, household goods, or domestic orindustrial premises, as sprays, fogs, dusts, smokes, wax-smears,lacquers, granules or baits, or in tricklefeeds to waterways, wells,reservoirs or other running or standing water.

The compounds of formula (I) are particularly useful for the control ofparasites of animals when applied orally, and in a further preferredaspect of the invention the compounds of formula (I) are used for thecontrol of parasites of animals by oral application. The compounds ofthe formula (I) or salts thereof may be administered before, during orafter meals. The compounds of th e formula (I) or salts thereof may bemixed with a carrier and/or foodstuff.

The compound of the formula (I) or salt thereof is administered orallyin a dose to the animal in a dose range generally from 0.1 to 500 mg/kgof the compound of the formula (I) or salt thereof per kilogram ofanimal body weight (mg/kg).

The frequency of treatment of the animal, preferably the domestic animalto be treated by the compound of the formula (I) or salt thereof isgenerally from about once per week to about once per year, preferablyfrom about once every two weeks to once every three months.

The compounds of the invention may be administered most advantageouslywith another parasiticidally effective material, such as anendoparasiticide, and/or an ectoparasiticide, and/or anendectoparasiticide. For example, such compounds include macrocycliclactones such as avermectins or milbemycins e.g., ivermectin, pyratel oran insect growth regulator such as lufenuron or methoprene.

The compounds of the formula (I) can also be employed for controllingharmful organisms in crops of known genetically engineered plants orgenetically engineered plants yet to be developed. As a rule, thetransgenic plants are distinguished by especially advantageousproperties, for example by resistances to particular crop protectionagents, resistances to plant diseases or pathogens of plant diseases,such as particular insects or microorganisms such as fungi, bacteria orviruses. Other particular properties concern, for example, the harvestedmaterial with regard to quantity, quality, storage properties,composition and specific constituents. Thus, transgenic plants are knownwhere the starch content is increased, or the starch quality is altered,or where the harvested material has a different fatty acid composition.

The use in economically important transgenic crops of useful plants andornamentals is preferred, for example of cereals such as wheat, barley,rye, oats, millet, rice, cassava and maize or else crops of sugar beet,cotton, soya, oilseed rape, potatoes, tomatoes, peas and other types ofvegetables.

When used in transgenic crops, in particular those which haveresistances to insects, effects are frequently observed, in addition tothe effects against harmful organisms to be observed in other crops,which are specific for application in the transgenic crop in question,for example an altered or specifically widened spectrum of pests whichcan be controlled, or altered application rates which may be employedfor application.

The invention therefore also relates to the use of compounds of theformula (I) for controlling harmful organisms in transgenic crop plants.

According to a further feature of the present invention there isprovided a pesticidal composition comprising one or more compounds ofthe invention as defined above, in association with, and preferablyhomogeneously dispersed in one or more compatible pesticidallyacceptable diluents or carriers and/or surface active agents [i.e.diluents or carriers and/or surface active.agents of the type generallyaccepted in the art as being suitable for use in pesticidal compositionsand which are compatible with compounds of the invention].

In practice, the compounds of the invention most frequently form partsof compositions. These compositions can be employed to controlarthropods, especially insects, or plant nematodes or mites. Thecompositions may be of any type known in the art suitable forapplication to the desired pest in any premises or indoor or outdoorarea. These compositions contain at least one compound of the inventionas the active ingredient in combination or association with one or moreother compatible components which are for example, solid or liquidcarriers or diluents, adjuvants, surface-active-agents, or the likeappropriate for the intended use and which are agronomically ormedicinally acceptable. These compositions, which may be prepared by anymanner known in the art, likewise form a part of this invention.

The compounds of the invention, in their commercially availableformulations and in the use forms prepared from these formulations maybe present in mixtures with other active substances such asinsecticides, attractants, sterilants, acaricides, nematicides,fungicides, growth regulatory substances or herbicides.

The pesticides include, for example, phosphoric esters, carbamates,carboxylic esters, formamidines, tin compounds and materials produced bymicroorganisms.

Preferred components in mixtures are:

1. from the group of the phosphorus compounds

acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, bromophos,bromophos-ethyl, cadusafos (F-67825), chlorethoxyphos, chlorfenvinphos,chlormephos, chlorpyrifos, chlorpyrifos-methyl, demeton,demeton-S-methyl, demeton-S-methyl sulfone, dialifos, diazinon,dichlorvos, dicrotophos, dimethoate, disulfoton, EPN, ethion,ethoprophos, etrimfos, famphur, fenamiphos, fenitriothion,fensulfothion, fenthion, flupyrazofos, fonofos, formothion, fosthiazate,heptenophos, isazophos, isothioate, isoxathion, malathion, methacrifos,methamidophos, methidathion, salithion, mevinphos, monocrotophos, naled,omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate,phorate, phosalone, phosfolan, phosphocarb (BAS-301), phosmet,phosphamidon, phoxim, pirimiphos, pirimiphos-ethyl, pirimiphos-methyl,profenofos, propaphos, proetamphos, prothiofos, pyraclofos,pyridapenthion, quinalphos, suiprofos, temephos, terbufos, tebupirimfos,tetrachlorvinphos, thiometon, tdazophos, trichlorphon, vamidothion;

2. from the group of the carbamates

alanycarb (OK-1 35), aldicarb, 2-sec-butylphenyl methylcarbamate (BPMC),carbaryl, carbofuran, carbosulfan, cloethocarb, benfuracarb,ethiofencarb, furathiocarb, HCN-801, isoprocarb, methomyl,5methyl-m-cumenylbutyryl (methyl)carbamate, oxamyl, pirimicarb,propoxur, thiodicarb, thiofanox,1-methylthio(ethylideneamino)-N-methyl-N-(morpholinothio)carbamate (UC51717), triazamate;

3. from the group of the carboxylic esters

acrinathrin, allethrin, alphametrin, 5-benzyl-3-furylmethyl(E)-(1R)-cis-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate,beta-cyfluthrin, alpha-cypermethrin, beta-cypermethrin, bioallethrin,bioallethrin ((S)-cyclopentylisomer), bioresmethrin, bifenthrin,(RS)-1-cyano-1-(6-phenoxy-2-pyridyl)methyl(1RS)-trans-3-(4-tert-butylphenyl)-2,2-dimethylcyclopropanecarboxylate(NCI 85193), cycloprothrin, cyfluthrin, cyhalothrin, cythithrin,cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate,fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin,fluvalinate (D isomer), imiprothrin (S-41311), lambda-cyhalothrin,permethrin, phenothrin (OR isomer), prallethrin, pyrethrins (naturalproducts), resmethrin, tefluthrin, tetramethrin, theta-cypermethrin,,tralomethrin, transfluthrin, zeta-cypermethrin (F-56701);

4. from the group of the amidines

amitraz, chlordimeform;

5. from the group of the tin compounds

cyhexatin, fenbutatin oxide;

6. others

abamectin, ABG-9008, acetamiprid, acequinocyl, Anagrapha falcitera,AKD-1022, AKD-3059, ANS-118, azadirachtin, Bacillus thuringiensis,Beauveria bassianea, bensultap, bifenazate, binapacryl, BJL-932,bromopropylate, BTG-504, BTG-505, buprofezin, camphechlor, cartap,chlorobenzilate, chlorfenapyr, chlorfluazuron,2-(4-chlorophenyl)4,5-diphenylthiophene (UBI-T 930), chlorfentezine,chlorproxyfen, chromafenozide, clothianidine,2-naphthylmethylcyclopropanecarboxylate (Ro12-0470), cyromazin, diacloden(thiamethoxam), diafenthiuron, DBI-3204, ethyl2-chloro-N-(3,5-dichloro-4-(1,1,2,3,3,3-hexafluoro-1-propyloxy)phenyl)carbamoyl)-2-carboximidate,DDT, dicofol, diflubenzuron,N-(2,3-dihydro-3-methyl-1,3-thiazol-2-ylidene)2,4-xylidine,dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, diofenolan,emamectin benzoate, endosulfan, ethiprole (sulfethiprole), ethofenprox,etoxazole, fenazaquin, fenoxycarb, fipronil, flonicamid (IKI-220),fluazuron, flumite (flufenzine, SZI-121),2-fluoro-5-(4-(4-ethoxyphenyl)-4-methyl-1-pentyl)diphenyl ether (MTI800), granulosis and nuclear polyhedrosis viruses, fenpyroximate,fenthiocarb, fluacrypyrim, flubenzimine, flubrocythrinate,flucycloxuron, flufenoxuron, flufenzine, flufenprox, fluproxyfen,gamma-HCH, halfenozide, halofenprox, hexaflumuron (DE_473), hexythiazox,HOI-9004, hydramethyinon (AC 217300), indoxacarb, ivermectin, L-14165,imidacloprid, indoxacarb (DPX-MP062), kanemite (AKD-2023), lufenuron,M-020, M-020, methoxyfenozide, milbemectn, NC-196, neemgard,nidinoterfuran, nitenpyram, 2-nitromethyl4,5-dihydro-6H-thiazine (DS52618), 2-nitromethyl-3,4-dihydrothiazole (SD 35651),2-nitromethylene-1,2-thiazinan-3-ylcarbamaldehyde (WL 108477),novaluron, pirydaryl, propargite, protrifenbute, pymethrozine,pyridaben, pydmidifen, pyriproxyfen, NC-196, NC-1111, NNI-9768,novaluron (MCW-275), OK-9701, OK-9601, OK-9602, OK-9802, R-195, RH-0345,RH-2485, RYI-210, S-1 283, S-1 833, SI-8601, silafluofen, silomadine(CG-177), spinosad, spirodiclofen, spiromesifen, SU-9118, tebufenozide,tebufenpyrad, teflubenzuron, tetradifon, tetrasul, thiacloprid,thiocyclam, thiamethoxam, tolfenpyrad, triazamate, triethoxyspinosyn A,triflumuron, verbutin, vertalec (mykotal), YI-5301.

Examples of suitable fungicide mixing partners may be selected in thefollowing list: aldimorph, amibromdole, ampropylfos potassium, andoprim,anilazine, azaconazole, azoxystrobin, benalaxyl, benodanil, benomyl,benthiavalicarb, benzamacril, benzamacril-isobutyl, bialaphos,binapacryl, biphenyl, bitertanol, blasticidin-S, boscalid,bromuconazole, bupirimate,;buthiobate, calcium polysulphide, capsimycin,captafol, captan, carbendazim, carboxin, carpropamid, carvon,chinomethionat, chlobenthiazone, chlorfenazole, chloroneb, chloropicrin,chlorothalonil, chlozolinate, clozylacon, cufraneb, cyazofamid,cyflufenamid cymoxanil, cyproconazole, cyprodinil, cyprofuram, debacarb,dichlorophen, diclobutrazole, diclocymet, diclofluanid, diclomezine,dicloran, diethofencarb, difenoconazole, diflumetorim dimethirimol,dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinocap,diphenylamine, dipyrithione, ditalimfos, dithianon, dodemorph, dodine,drazoxolon, edifenphos, epoxiconazole, etaconazole, ethaboxam,ethirimol, etridiazole, famoxadon, fenamidone, fenapanil, fenarimol,fenbuconazole, fenfuram, fenhexamid, fenitropan, fenoxanil; fenpiclonil,fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam,ferimzone, fluazinam, fludioxonil, flumetover, flumorph; fluoromide,fluopicolide, fluorofolpet, fluoxastrobin, fluquinconazole,flurprimidol, flusilazole, flusulphamide, flutolanil, flutriafol,folpet, fosetyl-aluminium, fosetyl-sodium, fthalide, fuberidazole,furalaxyl, furametpyr, furcarbonil, furconazole, furconazole-cis,furmecyclox, guazatine, hexachlorobenzene, hexaconazole, hymexazole,imazalil, imibenconazole, iminoctadine, iminoctadine albesilate,iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP),iprodione, iprovalicarb, irumamycin, isoprothiolane, isovaledione,kasugamycin, kresoxim-methyl, copper preparations, such as: copperhydroxide, copper naphthenate, copper oxychloride, copper sulphate,copper oxide, oxine-cpper and Bordeaux mixture, mancopper,mancozeb,)maneb, meferimzone, mepanipyrim, mepronil, metalaxyl-M,metconazole, methasulphocarb, methfuroxam, metiram, metomeclam,metominostrobin, metrafenone metsulphovax, mildiomycin, myclobutanil,myclozolin, nickel dimethyldithiocarbamate, nitrothal-isopropyl,nuarimol, ofurace, orysastrobin; oxadixyl, oxamocarb, oxolinic acid,oxpoconazole, oxycarboxim, oxyfenthiin, paclobutrazole, pefurazoate,penconazole, pencycuron, phosdiphen, phthalide, pimaricin, piperalin,picoxystrobin, polyoxin: polyoxorim, probenazole, prochloraz,procymidone, propamocarb, propanosine-sodium, propiconazole, propineb,proquinazid, prothioconazole, pyraclostrobin, pyrazophos, pyrifenox,pyrimethanil, pyroquilon, pyroxyfur, quinconazole, quinoxifen;quintozene (PCNB), silthiofam, simeconazole, spriroxamine, sulphur andsulphur preparations, tebuconazole, tecloftalam, tecnazene, tetcyclacis,tetraconazole, thiabendazole, thicyofen, thifluzamide,thiophanate-methyl, thiram, tiadinil, tioxymid, tolclofos-methyl,tolylfluanid, triadimefon, triadimenol, triazbutl, triazoxide,trichiamide, tricyclazole, tridemorph, trifloxystrobin, triflumizole,triforine, triticonazole, uniconazole, validamycin A, vinclozolin,viniconazole, zarilamide, zineb, ziram, zoxamide and also Dagger G,OK-8705, OK-8801, N-(3-ethyl-3,5,5-trimethyl-cyclohexyl)-3-formylamino-2-hydroxy-benzamide; N-(6-methoxy-3-pyridinyl)-cyclopropanecarboxamide;1-(1-naphthalenyl)-1H-pyrrole-2,5-dione;2,3,5,6-tetrachloro-4-(methylsulfonylypyridine;2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide;2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)3-pyridincarboxamide,N-(4-chlorophenyl)-N-ethyl4-methyl-2-nitrobenzenesulfonamide,

N-{2-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]ethyl}-2-(tdfluoromethyl)benzamide;

N-(3′,4′-dichloro-5-fluorobiphenyl-2-yl)-3-(difluoromethyly1-methyl-1H-pyrazole-4-carboxamide;

1-methyl-N-[3-(4-methylphenyl)-2-thienyl]-3-(trifluoromethyly1H-pyrazole-4-carboxamide;

3,4-dichloro-N-(2-cyanophenyl)isothiazole-5-carboxamide;

4-Chloro-alpha-propynyloxy-N-[2-[3-methoxy-4-(2-proynyloxy)phenyl]ethyl]-benzeneacetamide;

5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)[1,2,4]triazolo[1,5-a]pyrimidine.

The abovementioned components for combinations are known activesubstances, many of which are described in Ch.R Worthing, S. B. Walker,The Pesticide Manual, 12^(th) Edition, British Crop Protection Council,Farnham 2000.

The effective use doses of the compounds employed in the invention canvary within wide limits, particularly depending on the nature of thepest to be eliminated or degree of infestation, for example, of cropswith these pests. In general, the compositions according to theinvention usually contain about 0.05 to about 95% (by weight) of one ormore active ingredients according to the invention, about 1 to about 95%of one or more solid or liquid carriers and, optionally, about 0.1 toabout 50% of one or more other compatible components, such assurface-active agents or the like. In the present account, the term“carrier” denotes an organic or inorganic ingredient, natural orsynthetic, with which the active ingredient is combined to facilitateits application, for example, to the plant, to seeds or to the soil.This carrier is therefore generally inert and it must be acceptable (forexample, agronomically acceptable, particularly to the treated plant).

The carrier may be a solid, for example, clays, natural. or syntheticsilicates, silica, resins, waxes, solid fertilizers (for exampleammonium salts), ground natural minerals, such as kaolins, clays, talc,chalk, quartz, attapulgite, montmorillonite, bentonite or diatomaceousearth, or ground synthetic minerals, such as silica, alumina, orsilicates especially aluminium or magnesium silicates. As solid carriersfor granules the following are suitable: crushed or fractionated naturalrocks such as calcite, marble, pumice, sepiolite and dolomite; syntheticgranules of inorganic or organic meals; granules of organic materialsuch as sawdust, coconut shells, corn cobs, corn husks or tobaccostalks; kieselguhr, tricalcium phosphate, powdered cork, or absorbentcarbon black; water soluble polymers, resins, waxes; or solidfertilizers. Such solid compositions may, if desired, contain one ormore compatible wetting, dispersing, emulsifying or colouring agentswhich, when solid, may also serve as a diluent.

The carrier may also be liquid, for example: water; alcohols,particularly butanol or glycol, as well as their ethers or esters,particularly methylglycol acetate; ketones, particularly acetone,cyclohexanone, methylethyl ketone, methylisobutylketone, or isophorone;petroleum fractions such as paraffinic or aromatic hydrocarbons,particularly xylenes or alkyl naphthalenes; mineral or vegetable oils;aliphatic chlorinated hydrocarbons, particularly trichloroethane ormethylene chloride; aromatic chlorinated hydrocarbons, particularlychlorobenzenes; water-soluble or strongly polar solvents such asdimethylformamide, dimethyl sulphoxide, or N-methylpyrrolidone;liquefied gases; or the like or a mixture thereof.

The surface-active agent may be an emulsifying agent, dispersing agentor wetting agent of the ionic or non-ionic type or a mixture of suchsurface-active agents.

Amongst these are e.g., salts of polyacrylic acids, salts oflignosulphonic acids, salts of phenolsulphonic or naphthalenesulphonicacids, polycondensates of ethylene oxide with fatty alcohols or fattyacids or fatty esters or fatty amines, substituted phenols (particularlyalkylphenols or arylphenols), salts of sulphosuccinic acid esters,taurine derivatives (particularly alkyltaurates), phosphoric esters ofalcohols or of polycondensates of ethylene oxide with phenols, esters offatty acids with polyols, or sulphate, sulphonate or phosphatefunctional derivatives of the above compounds. The presence of at leastone surface-active agent is generally essential when the activeingredient and/or the inert carrier are only slightly water soluble orare not water soluble and the carrier agent of the composition forapplication is water. Compositions of the invention may further containother additives such as adhesives or colorants. Adhesives such ascarboxymethylcellulose or natural or synthetic polymers in the form ofpowders, granules or lattices, such as arabic gum, polyvinyl alcohol orpolyvinyl acetate, natural phospholipids, such as cephalins orlecithins, or synthetic phospholipids can be used in the formulations.It is possible to use colorants such as inorganic pigments, for example:iron oxides, titanium oxides or Prussian Blue; organic dyestuffs, suchas alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs;or trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum or zinc.

For their agricultural application, the compounds of the invention aretherefore generally in the form of compositions, which are in varioussolid or liquid forms. Solid forms of compositions which can be used aredusting powders (with a content of the compound of the invention,ranging up to 80%), wettable powders or granules (including waterdispersible granules), particularly those obtained by extrusion,compacting, impregnation of a granular carrier, or granulation startingfrom a powder (the content of the compound of the invention, in thesewettable powders or granules being between about 0.5 and about 80%).Solid homogenous or heterogenous compositions containing one or morecompounds of the invention, for example granules, pellets, briquettes orcapsules, may be used to treat standing or running water over a periodof time. A sirnilar effect may be achieved using trickle or intermittentfeeds of water dispersible concentrates as described herein.

Liquid compositions, for example, include aqueous or non-aqueoussolutions or suspensions (such as emulsifiable concentrates, emulsions,flowables, dispersions, or solutions) or aerosols. Liquid compositionsalso include, in particular, emulsifiable concentrates, dispersions,emulsions, flowables, aerosols, wettable powders (or powder forspraying), dry flowables or pastes as forms of compositions which areliquid or intended to form liquid compositions when applied, for exampleas aqueous sprays (including low and ultra-low volume) or as fogs oraerosols.

Liquid compositions, for example, in the form of emulsifiable or solubleconcentrates most frequently comprise about 5 to about 80% by weight ofthe active ingredient, while the emulsions or solutions which are readyfor application contain, in their case, about 0.01 to about 20% of theactive ingredient. Besides the solvent, the emulsifiable or solubleconcentrates may contain, when required, about 2 to about 50% ofsuitable additives, such as stabilizers, surface-active agents,penetrating agents, corrosion inhibitors, colorants or adhesives.Emulsions of any required concentration, which are particularly suitablefor application, for example, to plants, may be obtained from theseconcentrates by dilution with water. These compositions are includedwithin the scope of the compositions which may be employed in thepresent invention. The emulsions may be in the form of water-in-oil oroil-in-water type and they may have a thick consistency.

The liquid compositions of this invention, may, in addition to normalagricultural use applications be used for example to treat substrates orsites infested or liable to infestation by arthropods (or other pestscontrolled by compounds of this invention) including premises, outdooror indoor storage or processing areas, containers or equipment orstanding or running water.

All these aqueous dispersions or emulsions or spraying mixtures can beapplied, for example, to crops by any suitable means, chiefly byspraying, at rates which are generally of the order of about 100 toabout 1,200 liters of spraying mixture per hectare, but may be higher orlower (eg. low or ultra-low volume) depending upon the need orapplication technique. The compound or compositions according to theinvention are conveniently applied to vegetation and in particular toroots or leaves having pests to be eliminated. Another method ofapplication of the compounds or compositions according to the inventionis by chemigation, that is to say, the addition of a formulationcontaining the active ingredient to irrigation water. This irrigationmay be sprinkler irrigation for foliar pesticides or it can be groundirrigation or underground irrigation for soil or for systemicpesticides.

The concentrated suspensions, which can be applied by spraying, areprepared so as to produce a stable fluid product which does not settle(fine grinding) and usually contain from about 10 to about 75% by weightof active ingredient, from about 0.5 to about 30% of surface-activeagents, from about 0.1 to about 10% of thixotropic agents, from about 0to about 30% of suitable additives, such as anti-foaming agents,corrosion inhibitors, stabilizers, penetrating agents, adhesives and, asthe carrier, water or an organic liquid in which the active ingredientis poorly soluble or insoluble Some organic solids or inorganic saltsmay be dissolved in the carrier to help prevent settling or asantifreezes for water.

The wettable powers (or powder for spraying) are usually prepared sothat they contain from about 10 to about 80% by weight of activeingredient, from about 20 to about 90% of a solid carrier, from about 0to about 5% of a wetting agent, from about 3 to about 10% of adispersing agent and, when necessary, from about 0 to about 80% of oneor more stabilizers and/or other additives, such as penetrating agents,adhesives, anti-caking agents, colorants, or the like. To obtain thesewettable powders, the active ingredient is thoroughly mixed in asuitable blender with additional substances which may be impregnated onthe porous filler and is ground using a mill or other suitable grinder.This produces wettable powders, the wettability and the suspendabilityof which are advantageous. They may be suspended in water to give anydesired concentration and this suspension can be employed veryadvantageously in particular for application to plant foliage. The“water dispersible granules (WG)” (granules which-are readilydispersible in water) have compositions which are substantially close tothat of the wettable powders. They may be prepared by granulation offormulations described for the wettable powders, either by a wet route(contacting finely divided active ingredient with the inert filler and alittle water, e.g. 1 to 20% by weight, or with an aqueous solution of adispersing agent or binder, followed by drying and screening), or by adry route (compacting followed by grinding and screening).

The rates and concentrations of the formulated compositions may varyaccording to the method of application or the nature of the compositionsor use thereof. Generally speaking, the compositions for application tocontrol arthropod or plant nematode pests usually contain from about0.00001% to about 95%, more particularly from about 0.0005% to about 50%by weight of one or more compounds of the invention, or of total activeingredients (that is to say the compounds of the invention, togetherwith other substances toxic to arthropods or plant nematodes,synergists, trace elements or stabilizers). The actual compositionsemployed and their rate of application will be selected to achieve thedesired effect(s) by the farmer, livestock producer, medical orveterinary practitioner, pest control operator or other person skilledin the art.

Solid or liquid compositions for application topically to animals,timber, stored products or household goods usually contain from about0.00005% to about 90%, more particularly from about 0.001% to about 10%,by weight of one or more compounds of the invention. For administrationto animals orally or parenterally, including percutaneously solidor-liquid, compositions, these normally contain from about 0.1% to about90% by weight of one or more compounds of the invention. Medicatedfeedstuffs normally contain from about 0.001% to about 3% by weight ofone or more compounds of the invention. Concentrates or supplements formixing with feedstuffs normally contain from about 5% to about 90%,preferably from about 5% to about 50%, by weight of one or morecompounds of the invention. Mineral salt licks normally contain fromabout 0.1% to about 10% by weight of one or more compounds of formula(I) or pesticidally acceptable salts thereof.

Dusts or liquid compositions for application to livestock, goods,premises or outdoor areas may contain from about 0.0001% to about 15%,more especially from about 0.005% to about 2.0%, by weight, of one ormore compounds of the invention. Suitable concentrations in treatedwaters are between about 0.0001 ppm and about 20 ppm, more particularlyabout 0.001 ppm to about 5.0 ppm. of one or more compounds of theinvention, and may be used therapeutically in fish farming withappropriate exposure times. Edible baits may contain from about 0.01% toabout 5%, preferably from about 0.01% to about 1.0%, by weight, of oneor more compounds of the invention.

When administered to vertebrates parenterally, orally or by percutaneousor other means, the dosage of compounds of the invention, will dependupon the species, age, or health of the vertebrate and upon the natureand degree of its actual or potential infestation by arthropod orhelminth pests. A single dose of about 0.1 to about 100 mg, preferablyabout 2.0 to about 20.0 mg, per kg body weight of the animal or doses ofabout 0.01 to about 20.0 mg, preferably about 0.1 to about 5.0 mg, perkg body weight of the animal per day, for sustained medication, aregenerally suitable by oral or parenteral administration. By use ofsustained release formulations or devices, the daily doses required overa period of months may be combined and administered to animals on asingle occasion.

The following composition EXAMPLES 2A-2M illustrate compositions for useagainst arthropods, especially mites or insects, or plant nematodes,which comprise, as active ingredient, compounds of the invention, suchas those described in preparative examples. The compositions describedin EXAMPLES 2A-2M can each be diluted to give a sprayable composition atconcentrations suitable for use in the field. Generic chemicaldescriptions of the ingredients (for which all of the followingpercentages are in weight percent), used in the composition EXAMPLES2A-2M exemplified below, are as follows: Trade Name Chemical DescriptionEthylan BCP Nonylphenol ethylene oxide condensate SoprophorTristyrylphenol ethylene oxide condensate BSU Arylan CA A 70% w/vsolution of calcium dodecylbenzenesulfonate Solvesso 150 Light C₁₀aromatic solvent Arylan S Sodium dodecylbenzenesulfonate Darvan NO₂Sodium lignosulphonate Celite PF Synthetic magnesium silicate carrierSopropon T36 Sodium salts of polycarboxylic acids Rhodigel 23Polysaccharide xanthan gum Bentone 38 Organic derivative of magnesiummontmorillonite Aerosil Microfine silicon dioxide

Example 2A

A water soluble concentrate is prepared with the composition as follows:Active ingredient  7% Ethylan BCP 10% N-methylpyrrolidone 83%

To a solution of Ethylan BCP dissolved in a portion ofN-methylpyrrolidone is added the active ingredient with heating andstirring until dissolved. The resulting solution is made up to volumewith the remainder of the solvent.

Example 2B

An emulsifiable concentrate (EC) is prepared with the composition asfollows: Active ingredient 25% (max) Soprophor BSU 10% Arylan CA  5%N-methylpyrrolidone 50% Solvesso 150 10%

The first three components are dissolved in N-methylpyrrolidone and tothis is then added the Solvesso 150 to give the final volume.

Example 2C

A wettable powder (WP) is prepared with the composition as follows:Active ingredient 40% Arylan S  2% Darvan NO₂  5% Celite PF 53%

The ingredients are mixed and ground in a hammermill to a powder with aparticle. size of less than 50 microns.

Example 2D

An aqueous-flowable formulation is prepared with the composition asfollows: Active ingredient 40.00%  Ethylan BCP 1.00% Sopropon T360.0.20% Ethylene glycol 5.00% Rhodigel 230. 0.15% Water 53.65% 

The ingredients are intimately mixed and are ground in a bead mill untila mean particle size of less than 3 microns is obtained.

Example 2E

An emulsifiable suspension concentrate is prepared with the compositionas follows: Active ingredient 30.0% Ethylan BCP 10.0% Bentone 38  0.5%Solvesso 150 59.5%

The ingredients are intimately mixed and ground in a beadmill until amean particle size of less than 3 microns is obtained.

Example 2F

A water dispersible granule is prepared with the composition as follows:Active ingredient 30% Darvan No 2 15% Arylan S  8% Celite PF 47%

The ingredients are mixed, micronized in a fluid-energy mill and thengranulated in a rotating pelletizer by spraying with water (up to 10%).The resulting granules are dried in a fluid-bed drier to remove excesswater.

Example 2G

A dusting powder is prepared with the composition as follows: Activeingredient  1 to 10% Talc powder-superfine 99 to 90%

The ingredients are intimately mixed and further ground as necessary toachieve a fine powder. This powder may be applied to a locus ofarthropod infestation, for example refuse dumps, stored products orhousehold goods or animals infested by, or at risk of infestation by,arthropods to control the arthropods by oral ingestion. Suitable meansfor distributing the dusting powder to the locus of arthropodinfestation include mechanical blowers, handshakers or livestock selftreatment devices.

Example 2H

An edible bait is prepared with the composition as follows: Activeingredient 0.1 to 1.0% Wheat flour 80% Molasses 19.9 to 19%  

The ingredients are intimately mixed and formed as required into a baitform. This edible bait may be distributed at a locus, for exampledomestic or industrial premises, e.g. kitchens, hospitals or stores, oroutdoor areas, infested by arthropods, for example ants, locusts,cockroaches or flies, to control the arthropods by oral ingestion.

Example 2I

A solution formulation is prepared with a composition as follows: Activeingredient 15% Dimethyl sulfoxide 85%

The active ingredient is dissolved in dimethyl sulfoxide with mixing andor heating as required. This solution may be applied percutaneously as apour-on application to domestic animals infested by arthropods or, aftersterilization by filtration through a polytetrafluoroethylene membrane(0.22 micrometer pore size), by parenteral injection, at a rate ofapplication of from 1.2 to 12 ml of solution per 100 kg of animal bodyweight.

Example 2J

A wettable powder is prepared with the composition as follows: Activeingredient 50% Ethylan BCP 5% Aerosil 5% Celite PF 40%

The Ethylan BCP is absorbed onto the Aerosil which is then mixed withthe other ingredients and ground in a hammer-mill to give a wettablepowder, which may be diluted with water to a concentration of from0.001% to 2% by weight of the active compound and applied to a locus ofinfestation by arthropods, for example, dipterous larvae or plantnematodes, by spraying, or to domestic animals infested by, or at riskof infection by arthropods, by spraying or dipping, or by oraladministration in drinking water, to control the arthropods.

Example 2K

A slow release bolus composition is formed from granules containing thefollowing components in varying percentages (similar to those describedfor the previous compositions) depending upon need:

-   -   Active ingredient    -   Density agent    -   Slow-release agent    -   Binder

The intimately mixed ingredients are formed into granules which arecompressed into a bolus with a specific gravity of 2 or more. This canbe administered orally to ruminant domestic animals for retention withinthe reticulo-rumen to give a continual slow release of active compoundover an extended period of time to control infestation of the ruminantdomestic animals by arthropods.

Example 2L

A slow release composition in the form of granules, pellets, brickettesor the like can be prepared with compositions as follows: Activeingredient 0.5 to 25% Polyvinyl chloride  75 to 99.5% Dioctyl phthalate(plasticizer)

The components are blended and then formed into suitable shapes bymelt-extrusion or molding. These composition are useful, for example,for addition to standing water or for fabrication into collars oreartags for attachment to domestic animals to control pests by slowrelease.

Example 2M

A water dispersible granule is prepared with the composition as follows:Active ingredient 85% (max) Polyvinylpyrrolidone 5% Attapulgite clay 6%Sodium lauryl sulfate 2% Glycerine 2%

The ingredients are mixed as a 45% slurry with water and wet milled to aparticle size of 4 microns, then spray-dried to remove water.

Methods of Pesticidal Use

The following representative test procedure, using compounds of theinvention, was conducted to determine the parasiticidal activity ofcompounds of the invention.

Biological Examples

METHOD A: Screening Method to Test Systemicity of Compounds AgainstCtenocephalides felis (Cat Flea)

A test container was filled with 10 adults of Ctenocephalides felis. Aglass cylinder was closed on one end with parafilm and placed on top ofthe test container. The test compound solution was then pipetted intobovine blood and added to the glass cylinder. The treatedCtenocephalides felis were held in this artificial dog test (blood 37°C., 40-60% relative humidity; Ctenocephalides felis 20-22° C., 40-60%relative humidity) and assessment performed at 24 and 48 hours afterapplication. Compound 1-26, 2-50, 2-81, 2-87, 3-50, 4-03, 4-51, 5-13,546, 5-49, 5-52, 5-55, 5-67, 5-70, 5-73, 5-79, 8-15, 8-63, 942, 10-03gave at least 90% control of Ctenocephalides felis at a testconcentration of 5 ppm or less.

Method B: Screening Method to Test Contact Activity of Compounds AgainstCtenocephalides felis (Cat Flea)

Solutions of the test compounds were dropped onto filter paper, driedand the filter paper placed into test tubes and infested with 10 adultsof Ctenocephalides felis. The treated Ctenocephalides felis were held ina climate chamber (26° C., 80% RH) and the percentage efficacy assessed24 hours and 48 hours after application in comparison with the untreatedcontrol. Compounds of the invention gave useful contact control ofCtenocephalides felis at a test concentration of 1000 ppm.

METHOD C: Screening Method to Test Contact Activity AgainstRhipicephalus sanguineus (Brown Dog Tick)

Solutions of the test compounds were dropped onto filter paper, driedand the filter paper placed into test tubes and infested with 20-30larvae (LI) of Rhipicephalus sanguineus and the tubes closed with aclip. The treated Rhipicephalus sanguineus were held in a climatechamber (25° C., 90% RH) and the, percentage efficacy assessed 24 hoursafter application in comparison with the untreated control. Compoundnumbers 1-26, 4-03, 549 gave at least 70% contact control ofRhipicephalus sanguineus at a test concentration of 100 ppm.

METHOD D: Diabrotica undecimpunctata (Southern Corn Rootworm) Screen

Two days before application, seeds of maize were soaked in water underwarm conditions to elicit fast germination. One day before application,eggs of Diabrotica undecimpunctata were transferred to one half of aJapanese filter paper placed in a plastic petri dish. Afterwards, asprouted maize seed was placed on a moistened pad beside the filterpaper. Three drops of 200 microlitres of test compound solution werecarefully pipetted onto the egg. The remainder of the solution wasplaced on the maize and then the Petri dish was closed. The treated eggsin the Petri dishes were held in a climate chamber for 6 days. Thecompound efficacy (percentage of dead eggs and/or larvae in comparisonto untreated control) was assessed 6 days after application using abinocular microscope.

Compound number 381 gave at least 90% control of Diabroticaundecimpunctata at a test concentration of 10 ppm.

METHOD E: Nilaparvata lugens (Rice Brown Planthopper) Screen

The leaves of rice plants were dipped for 5 seconds into an aqueoussolution of the formulated preparation to be examined. After thesolution had run off, the rice plants were placed in a Petri dish andpopulated with about 20 larvae (L3 stage) of the rice leafhopper speciesNilaparvata lugens. The Petri dish was closed and then stored in aclimatized chamber (16 hours of light/day, 25° C., 40- 60% relativeatmospheric humidity). After. 6 days storage, the mortality among theleafhopper larvae was determined.

Compounds of the invention gave useful control of Nilaparvata lugens ata test concentration of 10 ppm.

METHOD F: Aphis fabae (Black Bean Aphid) Screen

Germinated field bean seeds (Vicia faba) with roots were transferredinto bottles filled with tap water. Aqueous solutions (4 ml) of theformulated preparation to be examined were dropped into the bottle. Theplants were then infested with approximately 100 black bean aphids(Aphis fabae) and stored in a controlled-environment cabinet atapproximately 25° C. After 3 and 6 days storage, the effect of thepreparation on the aphids was determined.

Compounds of the invention gave useful control of Aphis fabae at a testconcentration of 10 ppm.

1. A compound of formula (I):

wherein: R¹ is CN, CH₃, CF₃, CSNH₂ or C(=N-Z)—S(O)_(r)-Q; W is N orC—R⁸; R² and R⁸ are each independently halogen, CH₃ or NR⁹R¹⁰; R³ is(C₁-C₃)-haloalkyl, (C₁-C₃)-haloalkoxy or SF₅; R⁴ is hydrogen,(C₂-C₆)-alkenyl, (C₂-C₆)-haloalkenyl, (C₂-C₆)-alkynyl,(C₂-C₆)-haloalkynyl, (C₃-C₇)-cycloalkyl, CO₂-(C₁-C₆)-alkyl,CO₂—(C₃-C₆)-alkenyl, CO₂—(C₂-C₆)-alkynyl, CO₂—(CH₂),R¹¹,CO₂—(CH₂)_(m)R¹², CHO, CO—(C₃-C₇)-cycloalkyl, COR¹¹, COR¹², SO₂R¹³,(C₁-C₆)-alkyl or CO—(C₁-C₆)-alkyl, which last two mentioned groups areunsubsttuted or substituted by one or more R¹⁴ radicals; R⁵ is(C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₂-C₆)-alkenyl, (C₂-C₆)-haloalkenyl,(C₂-C₆)-alkynyl or (C₂-C₆)-haloalkynyl; A is (C₁-C₆)-alkylene or(C₂-C₆)-alkenylene which groups are unsubstituted or substituted by oneor more R¹⁶ radicals; or is (C₂-C₆)-alkylene in which 2, 3 or 4 adjacentcarbon atoms form a (C₃-C₇)-cycloalkyl ring, the (C₂-C₆)alkylene orformed (C₃-C₇)-cycloalkyl ring carbon atoms being unsubstituted orsubstituted by one or more radicals selected from the group consistingof (C₁-C₆)-alkyl and halogen; R⁶ and R⁷ are each independently H, R¹¹,R¹², (C₁-C₆)-alkyl, (C₂-C₆)alkenyl or (C₂-C₆)-alkynyl, which last threementioned groups are unsubstituted or substituted by one or moreradicals selected from the group consisting of halogen,(C₃-C₇)-cycloalkyl, R¹¹, R¹², (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, OR¹¹and OR¹²; or are each an acyl radical; or R⁶ and R⁷ together with theattached N atom form a four- to seven-membered saturated ring or a five-to seven-membered unsaturated ring, which ring optionally contains oneor more additional hetero atoms in the ring which are selected from O, Sand N, the ring being unsubstituted or substituted by one or moreradicals selected from the group consisting of halogen, (C₁-C₆)alkyl,(C₁-C₆)-haloalkyl and oxo, and when present any additional ring N atomis unsubstituted or substituted by a (C₁-C₆)-alkyl, CO—(C₁-C₆)-alkyl orCH₂R¹¹ radical; or R⁶ and R⁷ together with the attached N atom form aphthalimido radical which is unsubstituted or substituted by one or moreradicals selected from the group consisting of halogen, (C₁-C₆)-alkyland (C₁-C₆)-haloalkyl; or when A is (C₁-C₆)-alkylene, R⁷ together withthe attached N atom and A moiety form a four- to seven-memberedsaturated ring which is unsubstituted or substituted by one or moreradicals selected from the group consisting of halogen, (C₁-C₆)alkyl,(C₁-C₆)-haloalkyl and oxo, and R⁶ is H, (C₁-C₆)-alkyl, CH₂R¹¹,CO—(C₁-C₆)-alkyl or CO₂—(C₁-C₆)-alkyl; R⁹ and R¹⁰ are each independentlyH, (C₁-C₆)-alkyl, (C₂-C₆)-alkenyl or (C₂-C₆)-alkynyl, which last threementioned groups are unsubstituted or substituted by one or moreradicals selected from the group consistUng of halogen,(C₃-C₇)-cycloalkyl, R¹¹, R¹², (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, OR¹¹and OR¹²; R¹¹ is phenyl unsubstituted or substituted by one or moreradicals selected from the group consisting of halogen, (C₁-C₆)-alkyl,(C₁-C₆)-haloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, CN, NO₂,S(O)_(p)R¹⁷ and NR¹⁸R¹⁹; R¹² is heterocyclyl unsubstituted orsubstituted by one or more radicals selected from the group consistingof halogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,(C₁-C₄)-haloalkoxy, NO₂, CN, CO₂(C₁-C₆)-alkyl, S(O)_(p)R¹⁷, OH and oxo;R¹³ is (C₃-C₇)-cycloalkyl, (C₂-C₆)-alkenyl, (C₂-C₆)haloalkenyl,(C₂-C₆)-alkynyl, (C₂-C₆)-haloalkynyl, R¹¹ or R¹²; or is (C₁-C₆)-alkylunsubstituted or substituted by one or more R¹⁴ radicals; R¹⁴ ishalogen, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, (C₃-C₆)-alkenyloxy,(C₃-C₆-haloalkenyloxy, (C₃-C₆)-alkynyloxy, (C₃-C₆)-haloalkynyloxy,(C₃-C₇)-cycloalkyl, S(O)_(p)R¹⁶, CN, NO₂, OH, R¹¹, R¹², COR¹⁶, NR⁹R¹⁸,OR¹⁶ or CO₂R¹⁶; R¹⁵ is (C₃-C₇)-cycloalkyl, (C₂-C₆)-alkenyl,(C₂-C₆)-haloalkenyl, (C₂-C₆)-alkynyl, (C₂-C₆)-haloalkynyl, R¹¹ or R¹²;or is (C₁-C₆)-alkyl unsubstituted or substituted by one or more radicalsselected from the group consisting of halogen, (C₃-C₇)-cycloalkyl, R¹¹and R¹²; R¹⁶ is (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₂-C₆)-alkenyl,(C₂-C₆)-haloalkenyl, (C₂-C₆)-alkynyl, (C₂-C₆)-haloalkynyl,(C₃-C₇)-cycloalkyl, (C₃-C₇)-cycloalkyl-(C₁-C₄)-alkyl, (CH₂)_(q)R¹¹ or(CH₂)_(q)R¹²; R¹⁷ is (C₁-C₆)-alkyl or (C₁-C₆)-haloalkyl; R¹⁸ and R¹⁹ areeach independently H, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₆)-alkenyl,(C₃-C₆)-haloalkenyl, (C₃-C₆)-alkynyl, (C₃-C₇)-cycloalkyl or(C₃-C₇)-cycloalkyl-(C₁-C₆)-alkyl; or R¹⁸ and R¹⁹ together with theattached N atom form a five- or six-membered saturated ring whichoptionally contains an additional hetero atom in the ring which isselected from O, S and N, the ring being unsubstituted or substituted byone or more radicals selected from the group consisting of halogen,(C₁-C₆)-alkyl and (C₁-C₆)-haloalkyl; Z is H, (C₁-C₆)-alkyl,(C₁-C₆)-haloalkyl, (C₃-C₆)-alkenyl, (C₃-C₆)-alkynyl, (CH₂)_(q)R¹¹,COR¹⁷, CO₂—(C₁-C₆)-alkyl or S(O)_(p)R¹⁷; Q is (C₁-C₆)-alkyl or CH₂R¹¹;n, p and r are each independently zero, one or two; m and q are eachindependently zero or one; and each heterocyclyl in the above-mentionedradicals is independently a heterocyclic radical having 3 to 7 ringatoms and 1, 2 or 3 hetero atoms in the ring selected from the groupconsisting of N, O and S; or a pesticidally acceptable salt thereof. 2.A compound or a salt thereof as claimed in claim 1 wherein R¹ is CN. 3.A compound or a salt thereof as claimed in claim 1 wherein A is(C₁-C₆)-alkylene.
 4. A compound or a salt thereof as claimed in claim 1wherein: R¹ is CN; W is C-halogen; R² is halogen; R³ is CF₃, OCF₃ orSF₅; R⁴ is hydrogen, (C₂-C₆)-alkenyl, (C₂-C₆)-haloalkenyl,(C₂-C₆)-alkynyl, (C₂-C₆)-haloalkynyl, (C₃-C₇)-cycloalkyl,CO₂—(C₁-C₆)-alkyl, CO₂-(C₃-C₆)-alkenyl, CO₂—(C₂-C₆)-alkynyl,CO—(CH₂)_(m)R¹¹, CHO, CO—(C₃-C₇)-cycloalkyl, COR¹¹, SO₂R¹³,(C₁-C₆)-alkyl or CO—(C₁-C₆)-alkyl, which last two mentioned groups areunsubstituted or substituted by one or more R¹⁴ radicals; R⁵ is CF₃; Ais (C₁-C₆)-alkylene unsubstituted or substituted by one or more R¹⁶radicals, or (C₂-C₆)-alkenylene unsubstituted or substituted by one ormore radicals selected from the group consisting of (C₁-C₃)-alkyl,(C₁-C₃)-haloalkyl, (C₂-C₃)-alkenyl, (C₂-C₃)-alkynyl, (C₃-C₇)-cycloalkyl,(C₃-C₇)-cycloalkyl-(C₁-C₃)-alkyl and (CH₂)_(q)R¹¹; R⁶ and R⁷ are eachindependently H, R¹¹, (C₁-C₆)-alkyl, (C₂-C₆)-alkenyl or (C₂-C₆)-alkynyl,which last three mentioned groups are unsubstituted or substituted byone or more radicals selected from the group consisting of halogen,(C₃-C₇)-cycloalkyl, R¹¹, R¹², (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, OR¹¹and OR¹²; or are SO₂R¹⁵, CO₂—(C₃-C₆)-alkenyl, CO₂—(C₂-C₆)-alkynyl, CHO,CO—(C₃-C₇)-cycloalkyl, COR¹¹, COR¹², CO—(C₁-C₆)-alkyl orCO₂—(C₁-C₆)-alkyl, which last two mentioned groups are unsubstituted orsubstituted by one or more radicals selected from the group consistingof halogen, (C₃-C₇)-cycloalkyl, R¹¹ and R¹²; or R⁶ and R⁷ together withthe attached N atom form a four- to seven-membered saturated ring or afive- to seven-membered unsaturated ring, which ring optionally containsone or more additional hetero atoms in the ring which are selected fromO, S and N, the ring being unsubstituted or substituted by one or moreradicals selected from the group consisting of halogen, (C₁-C₃)-alkyl,(C₁-C₃)-haloalkyl and oxo, and when present any additional ring N atomis unsubstituted or substituted by a (C₁-C₆)-alkyl, CO—(C₁-C₆)-alkyl orCH₂R¹¹ radical; or R⁶ and R⁷ together with the attached N atom form aphthalimido radical which is unsubstituted or substituted by one or moreradicals selected from the group consisting of halogen, (C₁-C₆)-alkyland (C₁-C₆)-haloalkyl; or when A is (C₁-C₆)-alkylene, R⁷ together withthe attached N atom and A moiety form a four- to seven-memberedsaturated -ring which is unsubstituted or substituted by one or moreradicals selected from the group consisting of halogen, (C₁-C₆)-alkyl,(C₁-C₆)-haloalkyl and oxo, and R⁶ is H, (C₁-C₆)-alkyl, CH₂R¹¹,CO—(C₁-C₆)-alkyl or CO₂—(C₁-C₆)-alkyl; R⁹ is H, (C₂-C₃)-alkenyl,(C₂-C₃)-alkynyl or (C₁-C₃)-alkyl, which last mentioned group isunsubstituted or substituted by an R¹¹ radical; R¹¹ is phenylunsubstituted or substituted by one or more radicals selected from thegroup consisting of halogen, (C₁-C₃)-alkyl, (C₁-C₃)-haloalkyl,(C₁-C₃)-alkoxy, (C₁-C₃)-haloalkoxy, CN, NO₂, S(O)_(p)R¹⁷ and NR¹⁸R¹⁹;R¹² is heterocyclyl unsubstituted or substituted by one or more radicalsselected from the group consisting of halogen, (C₁-C₃)-alkyl,(C₁-C₃)-haloalkyl, (C₁-C₃)-alkoxy, (C₁-C₃)-haloalkoxy, NO₂, CN,CO₂(C₁-C₃)-alkyl, S(O)_(p)R¹⁷, OH and oxo; R¹³ is (C₃-C₇)-cycloalkyl,(C₂-C₃)-alkenyl, (C₂-C₃)-haloalkenyl, (C₂-C₃)-alkynyl,(C₂-C₃)-haloalkynyl, R¹¹ or R¹²; or is (C₁-C₃)-alkyl unsubstituted orsubstituted by one or more R¹⁴ radicals; R¹⁴ is halogen, (C₁-C₃)-alkoxy,(C₁-C₃)-haloalkoxy, (C₃-C₄)-alkenyloxy, (C₃-C₄)-haloalkenyloxy,(C₃-C₄)-alkynyloxy, (C₃-C₄)-haloalkynyloxy, (C₃-C₇)-cycloalkyl,S(O)_(p)R¹⁶, CN, NO₂, OH, R¹¹, R¹², COR¹⁶ NR⁹R¹⁸, OR¹⁶ or CO₂R¹⁶; R¹⁵ is(C₃-C₇)-cycloalkyl, (C₂-C₃)-alkenyl, (C₂-C₃)-haloalkenyl,(C₂-C₃)-alkynyl, (C₂-C₃)-haloalkynyl, R¹¹ or R¹²; or is (C₁-C₃)-alkylunsubstituted or substituted by one or more radicals selected from thegroup consisting of halogen, (C₃-C₇)-cycloalkyl, R¹¹ and R¹²; R¹⁶ is(C₁-C₃)-alkyl, (C₁-C₃)-haloalkyl, (C₂-C₄)-alkenyl, (C₂-C₄)-haloalkenyl,(C₂-C₄)-alkynyl, (C₂-C₄)-haloalkynyl, (C₃-C₇)-cycloalkyl,(C₃-C₇)-cycloalkyl-(C₁-C₃)-alkyl, (CH₂)_(q)R¹¹ or (CH₂)_(q)R¹²; R¹⁷ is(C₁-C₃)-alkyl or (C₁-C₃)-haloalkyl; R¹⁸ and R¹⁹ are each independentlyH, (C₁-C₃)alkyl, (C₁-C₃)-haloalkyl, (C₃-C₄)-alkenyl,(C₃-C₄)-haloalkenyl, (C₃-C₄)-alkynyl, (C₃-C₇)-cycloalkyl or(C₃-C₇)-cycloalkyl-(C₁-C₃)-alkyl; or R¹⁸ and R¹⁹ together with theattached N atom form a five- or six-membered saturated ring whichoptionally contains an additional hetero atom in the ring which isselected from O, S and N, the ring being unsubstituted or substituted byone or more radicals selected from the group consisting of halogen,(C₁-C₃)alkyl and (C₁-C₃)-haloalkyl; n and p are each independently zero,one or two; m and q are each independently zero or one; and eachheterocyclyl in the above-mentioned radicals is independently aheterocyclic radical having 3 to 7 ring atoms and 1, 2 or 3 hetero atomsin the ring selected from the group consisting of N, O and S.
 5. Acompound or a salt thereof as claimed in claim 1 wherein: R¹ is CN; W isC—Cl; R² is Cl; R³ is CF₃; R⁴ is hydrogen, (C₂-C₆)-alkenyl,(C₂-C₆)-alkynyl, CO₂—(C₁-C₆)-alkyl, CO—(CH₂)_(m)R¹¹, SO₂R¹³,CO—(C₁-C₆)-alkyl, CO—(C₁-C₆)-haloalkyl or (C₁-C₆)-alkyl, which lastmentioned group is unsubstituted or substituted by one or more R¹⁴radicals; R⁵ is CF₃; A is (C₁-C₅)-alkylene; R⁶ and R⁷ are eachindependently H, R¹¹, (C₂-C₆)-alkenyl, (C₂-C₆)-alkynyl or (C₁-C₆)-alkyl,which last mentioned group is unsubstituted or substituted by one ormore radicals selected from the group consisting of halogen,(C₃-C₆)-cycloalkyl, R¹¹, R¹², (C₁-C₆)-alkoxy and OR¹¹; or are SO₂R¹⁵,CO—(C₃-C₆)-cycloalkyl, COR¹¹, CO₂-(C₁-C₆)-alkyl or CO—(C₁-C₆)-alkyl,which last mentioned group is unsubstituted or substituted by one ormore radicals selected from the group consisting of halogen,(C₃-C₆)-cycloalkyl, R¹¹ and R¹²; or R⁶ and R⁷ together with the attachedN atom form a five- to seven-membered saturated ring or a five- toseven-membered unsaturated ring, which ring optionally contains one ormore additional hetero atoms in the ring which are selected from O, Sand N, the ring being unsubstituted or substituted by one or moreradicals selected from the group consisting of (C₁-C₆)-alkyl and oxo,and when present any additional ring N atom is unsubstituted orsubstituted by a (C₁-C₆)-alkyl, CO—(C₁-C₆)-alkyl or benzyl radical; orR⁶ and R7 together with the attached N atom form a phthalimido radicalwhich is unsubstituted or substituted by one or more radicals selectedfrom the group consisting of halogen, (C₁-C₃)-alkyl and(C₁-C₃)-haloalkyl; or when A is (C₁-C₅)-alkylene, R⁷ together with theattached N atom and A moiety form a five- to seven-membered saturatedring which is unsubstituted or substituted by one or more (C₁-C₆)-alkylradicals, and R⁶ is H, (C₁-C₆)-alkyl, CH₂R¹¹, CO—(C₁-C₆)-alkyl orCO₂—(C₁-C₆)-alkyl; R⁹ is H, (C₂-C₃)-alkenyl, (C₂-C₃)-alkynyl or(C₁-C₃)-alkyl, which last mentioned group is unsubstituted orsubstituted by an R¹¹ radical; R¹¹ is phenyl unsubstituted orsubstituted by one or more radicals selected from the group consistingof halogen, (C₁-C₃)-alkyl, (C₁-C₃)-haloalkyl, (C₁-C₃)-alkoxy,(C₁-C₃)-haloalkoxy, CN, NO₂, S(O)_(p)R¹⁷ and NR¹⁸R¹⁹; R¹² isheterocyclyl unsubstituted or substituted by one or more radicalsselected from the group consisting of halogen, (C₁-C₃)-alkyl,(C₁-C₃)-haloalkyl, (C₁-C₃)-alkoxy, (C₁-C₃)-haloalkoxy, NO₂, CN,CO₂(C₁-C₃)-alkyl, S(O)_(p)R¹⁷, OH and oxo; R¹³ is R¹¹ or R¹²; or is(C₁-C₃)-alkyl unsubstituted or substituted by one or more R¹⁴ radicals;R¹⁴ is halogen, (C₁-C₃)-alkoxy, (C₁-C₃)-haloalkoxy, (C₃-C₆)-cycloalkyl,S(O)_(p)R¹⁶, CN, NO₂, OH, R¹¹, R¹², COR¹⁶, NR⁹R¹⁸, OR¹⁶ or CO₂R¹⁶; R¹⁵is (C₃-C₆)-cycloalkyl, (C₂-C₃)-alkenyl, (C₂-C₃)-alkynyl or R¹¹; or is(C₁-C₃)-alkyl unsubstituted or substituted by one or more radicalsselected from the group consisting of halogen, (C₃-C₆)-cycloalkyl andR¹¹; R¹⁶ and R¹⁷ are each independently (C₁-C₃)-alkyl or(C₁-C₃)-haloalkyl; R¹⁸ and R¹⁹ are each independently H or(C₁-C₃)-alkyl; n and p are each independently zero, one or two; m iszero or one; and each heterocyclyl in the above-mentioned radicals isindependently a heterocyclic radical having 3 to 7 ring atoms and 1, 2or 3 hetero atoms in the ring selected from the group consisting of N, Oand S.
 6. A process for the preparation of a compound of formula (I) ora salt thereof as defined in claim 1 which process comprises: a) whereR¹ is CN, CH₃ or CF₃, and R², R³, R⁴, R⁵, R⁶, R⁷, W, A and n are asdefined in claim 1, alkylating a compound of formula (II):

wherein R¹ is CN, CH₃ or CF₃ and the other values are as defined inclaim 1, with a compound of formula (III):R⁶R⁷N-A-L   (III) wherein R⁶, R⁷ and A are as defined in claim 1, and Lis a leaving group; or b) where R¹ is CN, CH₃ or CF₃, and R², R³, R⁴,R⁵, R⁶, R⁷, W, A and n are as defined in claim 1, reacting a compound offormula (IV):

wherein L¹ is a leaving group and the other values are as defined inclaim 1, with a compound of formula (V):R⁶R⁷N—H   (V) wherein R⁶ and R⁷ are as defined in claim 1; or c) whereR¹ is CN, CH₃ or CF₃, and R², R³, R⁴, R⁵, R⁶, R⁷, W, A and n are asdefined in claim 1, reacting a compound of formula (VI):

wherein L² is a leaving group, and the other values are as defined inclaim 1, with a compound of formula (VII):R⁶R⁷N-A-NHR⁴   (VII) wherein R⁴, R⁶, R⁷ and A are as defined in claim 1;or d) where R¹ is CSNH₂, and R², R³, R⁴, R⁵, R⁶, R⁷, W, A and n are asdefined in claim 1, reacting the corresponding compound of formula (I)wherein R¹ is CN, with an alkali or alkaline earth metal hydrosulfide,or with H₂S in the presence of an organic base, or with the reagentPh₂PS₂; or e) where R¹ is CSNH₂, and R², R³, R⁴, R⁵, R⁶, R⁷, W, A and nare as defined in claim 1, reacting the corresponding compound offormula (I) wherein R¹ is CN, with a bis(trialkylsilyl)sulfide in thepresence of a base; or f) where R¹ is C(═N—H)—S-Q, and Q, R², R³, R⁴,R⁵, R⁶, R⁷, W, A and n are as defined in claim 1, reacting thecorresponding compound of formula (I) wherein R¹ is CSNH₂ with analkylating agent of formula (VIII) or (IX):Q-L³   (VIII)Q₃O⁺BF₄ ⁻  (IX) where Q is as defined in claim 1 and L³ is a leavinggroup; or g) where R¹ is C(═N-Z)-S-Q, Z is as defined in claim 1 withthe exclusion of H, and Q, R², R³, R⁴, R⁵, R⁶, R⁷, W, A and n are asdefined in claim 1, alkylating, acylating or sulfonylating thecorresponding compound of formula (I) wherein R¹ is C(═NH)—S-Q, with acompound of formula (X):Z-L⁴   (X) wherein Z is as defined in claim 1 with the exclusion of H,and L⁴ is a leaving group; or h) where R¹ is CN, CH₃ or CF₃, n is 1 or2, and R², R³, R⁴, R⁵, R⁶, R⁷, W and A are as defined in claim 1,oxidising the corresponding compound in which n is 0 or 1; and i) ifdesired, converting a resulting compound of formula (I) into apesticidally acceptable salt thereof.
 7. A pesticidal compositioncomprising a compound of formula (I) or a pesticidally acceptable saltthereof as defined in claim 1 in association with a pesticidallyacceptable diluent or carrier and/or surface active agent.
 8. A methodfor controlling pests at a locus which comprises applying thereto aneffective amount of a compound of formula (I) or a salt thereof asclaimed in claim
 1. 9. A method for controlling pests at a locus whichcomprises applying thereto an effective amount of a composition of claim7.